When I played FO3 on my PC there was a way to bind items to keys ...i.e #1 10mm, #2 Stimpack etc.. On the Ps3 for NV pipboy it looks like there is a screen with similar functionality but I don't know how it works. Does it work and if so, how?

When in the Pipboy press the corresponding key that says "hotkey". I believe it's R2. Then 9 boxes will appear; select a box to place an item in. Then in real time press the corresponding direction on the D-pad (i.e. top center of hot key = up D-pad arrow). I would only recommend the center ones though, not the diagonal boxes as I have no clue how to access those in real time.

Ah, TYVM.