Because you have mixed numerical and string data, you have to make your variable w a cell array if you just want to run xlswrite() once. One way to come up with the cell array with your desired format for numerical data is below.
Num1=[1,2.32322232,4;222,0,-Inf];
char1=['A1';'A2'];
w=textscan(sprintf('%10.2f,',Num1),'%s','delimiter',',');
w=[cellstr(char1), reshape(w{1},size(Num1,1),size(Num1,2))];
xlswrite('ExcelFile.xls',w);
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