That is what I was thinking I would have to do. Maybe I will try my hand at the G.E.C.K. and make a White room to do the poses so I can use photoshop and make the flats. I just hope I can get the back shots from a proper angle unless there is a console control that will allow me to rotate them 180 degrees.
Is there anyway of being able to do the same thing enemies? Like Super Mutants, Deathclaws and stuff?
The engine (unlike real life photos, makes a clear contrasting line between figure and back ground; most of the time), you could use the Magnetic selection to isolate the poses from a screenshot and certainly do this with enemies like Deathclaws. With these images, its a lot easier than you'd expect.
* Although... the 3d modeler method is more controlled, and can achieve any result you'd like. http://i271.photobucket.com/albums/jj125/Gizmojunk/deathclawAVnma.gif
Spoiler If you watch him close, he will drink the tea eventually.
Edit: I would try just using a standard [test] worldspace from the game. Load up an invulnerable PC, and spawn an enemy and record them with Fraps (both video and screen capture). See what results you get, and carve out the enemies in Photoshop. Later, you can construct the few poses you don't get in a modeler or by selectively pausing the game to catch screen shots of NPCs in mid action; but in a pose that's "close enough" to what you want.
Afterward, you can composite the NPCs over any screenshot background you wish.