Which did you see? Blocking spells or shooting projectiles that are in mid-air?
It could have been omzy's spell deflection mod. Basically you can deflect the spell back at his caster if your block skill is high enough, or you can decide to shoot somebody else. When you're not good enough, you either don't block it or the spell goes in the ceiling, floor, etc. Quite a neat mod that has never left my load order since I tested it.
http://cs.elderscrolls.com/constwiki/index.php/User:Omzy
http://tesnexus.com/downloads/file.php?id=11477
edit: I remember that in morrowind you could also block incoming spells with arrows