Adobe Video Workshop looks really cool, it has videos showing how to do lots of neat things in CS3.
For a long time, I stuck to my GPL guns and used Inkscape exclusively. I did the whole peeridol.com site in Inkscape, doing all the slicing and designing by hand.
However, my new collaborator, Jennifer Derton does her graphic designs in Adobe Illustrator CS2, and although Inkscape worked admirably when loading in Illustrator SVG files, there were some strange lingering colour matching issues and other little problems. So, for now, I'm using Illustrator. I'm really happy with it, it has a lot of powerful things.
My plan is to learn Illustrator really well, and then, in the future when I have more time, to integrate some of the powerful Illustrator features back into Inkscape, because Inkscape rocks, and if it just had better colour matching and stuff, it would be perfect.