Tough to pick a single fave, so I'll do 10...
1. Bespin Capture Han Solo - finally a Bespin Han with decent proportions (ie, not POTF2 He-Man proportions, tho the monkey arms bugged some)! And he could strike the "blasting Vader" pose! And he had a proper short-scope blaster in his holster (albeit gray instead of black)...
2. Bespin Guard - While flawed (open coat, odd likeness, etc) he had a TON of accessories and could wear them all at once!
3. Security Battle Droid - a nice sculpt, well-articulated while still being skinny (the lever was the only silly part), and I think he's the only Battle Droid sculpted to be able to PROPERLY hold his blaster in both hands! Even TVC's Battle Droid can't do that, really (bendy enough to do it, but it looks awkward).
4. Dagobah Vader - decent articulation, nice sculpt, well-executed removable facemask, a nice two-handed saber pose, nice translucent 'phantom' effect.
5. Mon Cala Officer - basically a repaint of POTF2 Ackbar, he was different enough to make him really appealing: he could HOLD accessories, unlike Ackbar, and he had a unique pistol and helmet.
6. Tessek - like others, 'Squid-Head' was a favorite Vintage figure and POTJ Tessek is pretty nice. Low on articulation, he was still a great sculpt and had a nice pistol/holster deal, especially nice since the pistol was sculpted to be reminiscent of his vintage gray blaster but NOT just a DH-17 Rebel Fleet Trooper blaster, which is what that vintage pistol sculpt was meant to be.
7. Qui-Gon Jinn, Jedi Training Gear - low on articulation, it was still an awesome outfit based on concept art. Closer to the kinds of outfits I expected we might see on Jedi in the PT, rather than just "Kenobi Tatooine gear with skirts of various lengths".
8. BoShek - I really want an SA upgrade of him, with a swappable 'helmet holding' hand so you can recreate his POTJ pose. Another thing I liked besides the character was his pistol: first time we got that SR-combat pistol in the line (aside from some POTF2-scale monstrosity, perhaps). The pistol was a little too small, but it's much nicer than the gigantic ones that have come with most TIE Pilots in recent years as well as Ponda Baba & Evazan.
9. Cold-Weather Gear Obi-Wan - again low on articulation, he's just too reminiscent of vintage Hoth Han to not love him. Blue coat, a backpack, a removable helmet. Just a fun 'offscreen adventure' figure. The Clone Wars' cold-weather Obi-Wan (OR Anakin!) aren't nearly as neat.
10. Ellors Madak - Mr. Pegwarmer, if he'd had more articulation I'd have snapped up several for custom fodder. I was thrilled to finally get a Duros, especially after seeing them tarnished with their cousin-species the Neimoidians in '99. Duros have an EU history of being among the oldest travelers among the stars, and I always equated that with them being a very populous race ala humans in the GFFA... EU, however, hasn't matched my expectations. I love seeing Duros characters pop up, and it doesn't happen nearly enough. Too many humans, IMO...