I almost always shave at night, before bed. It's part of my routine now and, thanks to DE, I'm still BBS when I wake up and only get minor stubble towards the end of the day. I love having the time at night for a relaxing shave.
Though I've been on vacation the past week, and have had the luxury of shaving in the morning after my shower. I like it a lot and fully intend to go back to mornings when I retire. Or maybe if I can find a law firm that offers a swing or graveyard shift.
I usually shave in the evening about 2000-2030hrs.
I find that it helps me to wind down a little after being at work during the day. It's 30mins of 'ME TIME' that I treasure, just as long as my step-lad doesn't decide to come and talk at me when shaving
On the occasions that I work nights then I usually shave around 1400-1500hrs before leaving for work. I'm lucky in that for the most part my job doesn't require me to be clean shaven all the time so I can get away with not doing it if I want.
I shave in the AM in the shower. I also make my own hours at work so I leave the house late and shave later in the AM also. This gives me time to wake up and enjoy my shave without rushing now that I actually enjoy shaving.