Can you put Robo Substitute on your Bench or make it your Active Pokemon during game startup?
No, you cannot. This is an Item card before it is in play, so you cannot put this card out as a Pokemon when you are preparing for battle.
Source: Phantom Forces FAQ (2014-11-13), TPCi Rules Team (2014-11-13)

Relevant cards

Note: All applicable cards may not be listed below.
XY4_102