I'd vote for PostgreSQL multiple times if I could. I'm a consultant DBA (-ish; I do other stuff as well, but that's what puts most of the food on my table), and have multiple clients using pg.
Why do you use pgsql over mysql? I've used mysql a lot, and pgsql a little. I can't tell the difference, other than pgsql being slower and having less support. Some people swear by it, so I'm curious what I am missing.
In performance terms, granted, pg was a bit of a dog in those days, but it outperformed MySQL in every benchmark I could throw at it, with minimal tuning. So, if you're experiencing it as less performant, you're most likely running with a default configuration — which is deliberately tuned for something like a 486-class box with 128MB RAM or so — and/or haven't ANALYZEd your data. (Those are complete WAGs, knowing nothing more than what you've said about your scenario, but they tend to be among the more common reasons for lackluster performance.)
As for support, as a complete noob, I had a weird performance problem I couldn't make sense of, so I went to the mailing lists. Within a few hours, I was exchanging stack traces and other sundry debugging/profiling dumps with Tom Lane. (He's in the Wikipedia. Even if you've never touched PostgreSQL, you use his code every day of your life.) I don't think you can get much better support than that. Since, I've never encountered a problem that I haven't been able to have addressed, or at least get pointed in the right direction, by asking on — or searching the archives of — the relevant mailing list.
From there, it was largely a matter of, "This is the one I already know how to use...", along with the better feature-set (not mentioned by any of the sibling posts thus far: transactional DDL); the lack of a known-evil corporate overlord who could pull the plug at any time; the consistent tens-of-percent performance improvements in every major release; a development community that will punt a feature to the next release if it's not 100% ready and provably correct; and, let's be honest, the fact that, as someone who's been doing pg work for as long as I have, I can command a very comfortable hourly rate on the basis of that depth of experience — particularly when it's been focused in high availability and replication.
(EDIT: proofreading.)