Some people are turned off by Villarrica's popularity and Pucón's touristic nature. I think that's pretty silly. Villarrica is one of my favorite ski experiences! There's a lot to love about this mountain and area.
First of all, it's a 5000-foot ascent and descent, which makes for a great day of skiing. To arrive to the top requires about five-hours under most conditions. We normally are able to use skins for at least half the ascent and then switch to boot crampons on fairly easy terrain. Sometimes we can nearly skin to the top and sometimes there's a section where we need ski crampons. But it's always pretty straightforward.
The summit is one of the most dramatic mountain tops I have ever been on. A smoking volcano! The crater is a few hundred feet deep and on a good day you can look down into it. It's like something out of Star Wars.
The descent is world-class. Even if it is the most popular peak in Chile, I can't remember ever crossing a track on this mountain. It is huge. It normally serves up some of the silkiest corn snow in the world and for a long descent. 5000-feet of world-class skiing! There are gentle slopes and steep walls to play on.
Pucón is definitely developed and touristy; but in September and October it's a manageable pace. Mostly empty, we get the benefits of amazing hot springs and great restaurants all to ourselves. After a season or even just a week of traveling in Chile, it can be nice to hang in a place that feels a little more like home.
I know it's not a very original answer, but when people ask me which is my favorite volcano for skiing, I have to put Villarrica high on the list. It's a big descent of good skiing with great food and amazing hot springs at its base. What more could you want?