We had quite an active vector community a few years ago with great artists such as donbenni (who made several very useful tutorials for tooning/vectoring in Photoshop, check his deviantart), under18carbon, stumpydino and suzq. Photoshop isn't really a vector program but there is a way to re-create the scalability they possess (again, donbenni did a great tut on that). Personally I use Illutstrator as I feel that you can manipulate paths easier.