In mathematical logic you have to be very careful how you phrase things. The "theory of the real numbers" is complete almost by definition, since it is the set of sentences in the language of fields which hold true in $\mathbb{R}$. (Moreover, in this sense the theory of $\mathbb{N}$ is also complete!)
What you want is that the theory of real numbers is decidable, i.e., there is an algorithm to determine whether a given sentence in the language of fields holds in $\mathbb{R}$. This follows from the completeness of the theory of real closed fields, which is a celebrated result of Tarski. Most introductions to model theory discuss this result and give a proof, including these lecture notes of mine: please see $\S 3.8$.
Added: A primary source is
A. Tarski, A Decision Method for Elementary Algebra and Geometry. RAND Corporation,
Santa Monica, Calif., 1948.
Preamble
I believe that the OP is seeking a characterization of $ \mathbb{Q} $ using only the first-order language of fields, $ \mathcal{L}_{\text{Field}} $. Restricting ourselves to this language, we can try to uncover new axioms, in addition to the usual field axioms (i.e., those that relate to the associativity and commutativity of addition and multiplication, the distributivity of multiplication over addition, the behavior of the zero and identity elements, and the existence of a multiplicative inverse for each non-zero element), that describe $ \mathbb{Q} $ uniquely.
Any attempt to describe the smallest field satisfying a given property must prescribe a method of comparing one field with another (namely using field homomorphisms, which are injective if not trivial), but such a method clearly cannot be formalized using $ \mathcal{L}_{\text{Field}} $.
1. There Exists No First-Order Characterization of $ \mathbb{Q} $
The answer is ‘no’, if one is seeking a first-order characterization of $ \mathbb{Q} $. This follows from the Upward Löwenheim-Skolem Theorem, which is a classical tool in logic and model theory.
Observe that $ \mathbb{Q} $ is an infinite $ \mathcal{L}_{\text{Field}} $-structure of cardinality $ \aleph_{0} $. The Upward Löwenheim-Skolem Theorem then says that there exists an $ \mathcal{L}_{\text{Field}} $-structure (i.e., a field) $ \mathbb{F} $ of cardinality $ \aleph_{1} $ that is an elementary extension of $ \mathbb{Q} $. By definition, this means that $ \mathbb{Q} $ and $ \mathbb{F} $ satisfy the same set of $ \mathcal{L}_{\text{Field}} $-sentences, so we cannot use first-order logic to distinguish $ \mathbb{Q} $ and $ \mathbb{F} $. In other words, as far as first-order logic can tell, these two fields are identical (an analogy may be found in point-set topology, where two distinct points of a non-$ T_{0} $ topological space can be topologically indistinguishable). However, $ \mathbb{Q} $ and $ \mathbb{F} $ have different cardinalities, so they are not isomorphic. This phenomenon is ultimately due to the fact that the notion of cardinality cannot be formalized using $ \mathcal{L}_{\text{Field}} $. Therefore, any difference between the two fields can only be seen externally, outside of first-order logic.
2. Finding a Second-Order Characterization of $ \mathbb{Q} $
This part is inspired by lhf's answer below, which I believe deserves more credit. We start by formalizing the notion of proper subfield using second-order logic.
Let $ P $ be a variable for unary predicates. Consider the following six formulas:
\begin{align}
\Phi^{P}_{1} &\stackrel{\text{def}}{\equiv} (\exists x) \neg P(x); \\
\Phi^{P}_{2} &\stackrel{\text{def}}{\equiv} P(0); \\
\Phi^{P}_{3} &\stackrel{\text{def}}{\equiv} P(1); \\
\Phi^{P}_{4} &\stackrel{\text{def}}{\equiv} (\forall x)(\forall y)((P(x) \land P(y)) \rightarrow P(x + y)); \\
\Phi^{P}_{5} &\stackrel{\text{def}}{\equiv} (\forall x)(\forall y)((P(x) \land P(y)) \rightarrow P(x \cdot y)); \\
\Phi^{P}_{6} &\stackrel{\text{def}}{\equiv} (\forall x)((P(x) \land \neg (x = 0)) \rightarrow (\exists y)(P(y) \land (x \cdot y = 1))).
\end{align}
What $ \Phi^{P}_{1},\ldots,\Phi^{P}_{6} $ are saying is that the set of all elements of the domain of discourse that satisfy the predicate $ P $ forms a proper subfield of the domain. The domain itself will be a field if we impose upon it the first-order field axioms. Hence,
$$
\{ \text{First-order field axioms} \} \cup \{ \text{First-order axioms defining characteristic $ 0 $} \} \cup \{ \neg (\exists P)(\Phi^{P}_{1} ~ \land ~ \Phi^{P}_{2} ~ \land ~ \Phi^{P}_{3} ~ \land ~ \Phi^{P}_{4} ~ \land ~ \Phi^{P}_{5} ~ \land ~ \Phi^{P}_{6}) \}
$$
is a set of first- and second-order axioms that characterizes $ \mathbb{Q} $ uniquely because of the following two reasons:
Up to isomorphism, $ \mathbb{Q} $ is the only field with characteristic $ 0 $ that contains no proper subfield.
If $ \mathbb{F} \ncong \mathbb{Q} $ is a field with characteristic $ 0 $, then $ \mathbb{F} $ does not model this set of axioms. Otherwise, interpreting “$ P(x) $” as “$ x \in \mathbb{Q}_{\mathbb{F}} $” yields a contradiction, where $ \mathbb{Q}_{\mathbb{F}} $ is the copy of $ \mathbb{Q} $ sitting inside $ \mathbb{F} $.
Best Answer
I'm going to consider three questions:
What does the existence of the real numbers is needed?
Let $r$ be an odd number such that $r^2$ is even...
Consider a triangle with four sides...
Any reasoning which starts with the sentences above is nonsense because such a number and such a triangle don't exist. Analogously, if $\mathbb{R}$ (defined as an complete ordered field) did not exist (i.e. if there were no structure satisfying the axioms of complete ordered field) then the analysis course would be nonsense. This is why the proof of the existence is needed, to show that we are indeed doing something instead of nothing.
What does existence of the real numbers mean?
Real Analysis can be viewed as an axiomatic theory. In this context, the proof of the existence of $\mathbb{R}$ (i.e. the construction of a complete ordered field) means that there is a model for the axioms of a complete ordered field and thus the theory (i.e. the real analysis) is consistent.
Why would we need the completeness axiom?
Without the completeness axiom we cannot do analysis. Take, for example, $\mathbb Q$. It satisfies all axioms that defines a complete ordered field except the completeness axiom and nevertheless is inadequate for analysis.