I personally use MySQLi.
The only differences that I know between the two is how you bind params during a query, other than that, I don't know anything major MySQL wise. However, PDO supports more than just MySQL, so that's a plus for people who use something else, but that's all I can think of.
Personally I think both are pretty good, although this can give you an idea. Extracted fromYou must be registered for see links
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So here basically you should go for MySQLi in my opinion, but a plus for PDO is that you can use it for almost any database driver ( Oracle, SQLite, MySQL, Ms SQL, PostGre, IBM ) which is pretty cool and neat.
So, it's up to you to decide - You can always go hardcore and use both ( So awesome, do it for Rev3 can explain you how on MSN )