I've only done this once. On my first Generation V game. When I caught Joltik, I pressed B every time she attempted to evolve in Gavantula. I made a promise when I started that save. "I will not evolve my Joltik." Obviously I discovered the repercussions of not letting her evolve, especially during the Elite Four encounters >_>. Anyway, now I have her in Black 2, still there looking cute as a button. While I was training her to level 100 in Black 2, there were several times I almost threw in the towel and let her evolve. But at the last moment, I had a change of heart and hit B again. Forever my Joltik. :'3
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