Those who commented in favor of postgres: What are some of the biggest deployments of postgres? Facebook has a gargantic deployment of MySQL and it just works. The author of the answer on Quora mentions reliable scalability as the most important factor for their MySQL choice on another answer here: http://bit.ly/dm6HtQ . What is the biggest system that postgres is deployed in?
A few observations:
1) MyISAM's performance is highly dependent on certain idiosyncrasies of a lot of applications. Using MyISAM in this day and age is a very bad idea. InnoDB at least gets closer to real database behavior.
2) The "query optimizer" is insulting at best and actively impeding getting things right if you use it for much more than simple queries. Something that's more along the lines of what really large databases (as opposed to KV stores) get used for can implode the server.
Personally, I think too many people try and stick things in relational databases that don't belong there simply because they've got the hammer in their hand and it's easier than pulling out a screwdriver.