Ideally, efficiency speaking, series up batteries to sufficiently higher than you need which will still be higher than you need when "flat", then use a buck converter to go down to 5v. 8 AA cells in series will be 12v full 6.4v empty.
Thats ideally speaking, because buck is a bit more efficient than boost. But the practicality is that efficiency of a converter depends on so many things that it really isn't going to matter what you choose, boost, or buck (or sepic, or cuk or....), you are going to get somewhere in the area of 75 - 95% efficiency.
So the answer is less to do with efficiency, and more whatever is most convenient for the capacity you require - how many cells do you want to fit in to your space and what cell holders are available to fit that space, is most likely to dictate your choice.