do you want the nice answer or the mean answer? i'll give you both--
mean answer: go read shiv's description, find out it is an instant attack with an offhand, and stop asking dumb questions.
nice answer: yes it sure could and shiv is a great tool in pvp for mace spec rogues (can proc combat potency and mace stun). watch out, though, because shiv'ing most likely (depends on gear i guess) won't yield higher damage than sinister strike. only shiv if you have some crazy (and probably) inefficient envenom build.