I used both for many years (80% for web applications), and I love both, but I should say use the one that your prefer, both are great database, both can fit on 90% of cases, but there is still some good/bad points for each.
If you want (easy) replication, go to MySQL, for now, replication on Postgresql is the hell to manage and monitor (and I don't think the stream replication (9.0) will change something, it's still very light on the administration/monitoring side), same thing if you want clustering.
MySQL also allow some things that are missing on PostgreSQL: Partitioning (PostgreSQL "cheats" to simulate partitioning), a Query Cache that can be really useful on read-massive applications, the Event Scheduler (okay it's pretty basic on MySQL but it do it's job !)
the REPLACE statement can also be useful, it's missing on PostgreSQL.
On the other side, PostgreSQL also have some good advantages, you can create your custom data type, you have better backup systems (custom smaller format, but YES on MySQL you CAN do coherent backups with InnoDB WITHOUT locking), you can create almost anything you want with UDF (you can use a lot of language), for GIS database, PostgreSQL is also better (but there is some "cheating" that make is harder to use).
Just take a look on the features that you want, if it's missing on PostgreSQL, choose MySQL, if it's missing on MySQL, choose PostgreSQL.