For precise control, plot it yourself with bar() and then set the 'EdgeColor' and 'FaceColor' properties in the bar() function:
img = imread('moon.tif');
[counts, grayLevels] = imhist(img, 64);
bar(grayLevels, counts, 'EdgeColor', 'r', 'FaceColor', 'c', 'BarWidth', 0.95);
Makes cyan bars with red outlines.
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