oi.
err...so...I take it you LIKED Curse of Chalion?
If you liked that, definitely read the next one, Paladin of Souls. Its main character is Ista, who had a pretty minor role in Chalion. The main characters of Chalion do not appear (except for those pesky gods!). It's got so many great moments. My favorite is when she meets the middle-aged woman's romance-novel dreamboat of a man, and then finds out...well...ha ha ha ha ha!
I also really liked her first fantasy novel, The Spirit Ring. I can't definitely say you'd like it, but the main characters are young rather than middle-aged like the ones in Paladin.
My favorite...well, I'm a sucker for emotional books. The end of the first half of Chalion is the most emotionally intense thing I've ever read. The end of Shards of Honor also makes me cry every time (though in a good way). So I definitely recommend Shards of Honor. Nowadays it's in the omnibus edition Cordelia's Honor, which contains the sequel Barrayar, but the two books flow together very nicely, even though Barrayar was written years later. I'd definitely say both, but maybe it's better to space them out in order to give the full effect to the first book.
Shards of Honor is the first Vorkosigan book (which are science fiction and not fantasy), though most of the rest star the next generation (except, well, Falling Free happens a couple hundred years beforehand in the same universe). But it's a genuine space opera romance novel. After Barrayar there's not much romance until you get to Komarr (unless you count Cetaganda, which has some unrequited stuff).
Not sure why I'm focusing on romance though. The romance in Chalion is kind of thrown in at the end (something I thought one of its weak points). So maybe you're just looking for creative worldbuilding, plotting, and great characters? Well, read the ones I suggested first.
I'd say Bujold's greatest strength is very much her characters. She's got some interesting worldbuilding and plotting as well, but the character dynamics are definitely the biggest draw for me.
Aaaaah, making myself want to go back and read all the books again. I love them all. She read parts of 2 chapters of the 3rd Chalion-universe book at Worldcon, and it was good good good.
