Just did some tinkering as I'm actually benchmarking sqlite with PDO and then switched to mysql for a laugh - the standard pdo extension must be before the mysql one for it to work - so in php.ini
extension=php_pdo.dll
extension=php_pdo_mysql.dll
But this will cause a startup error
extension=php_pdo_mysql.dll
extension=php_pdo.dll
Can you give that a go? Don't just wack the mysql line in at the top of the ini file, which you might have done.