The php_pdo_mysql.dll in the extension directory may be trying to load the libmysql.dll or mysql.dll which by default is in the php directory (I think - they are at least in my php directory but I installed it so long ago I can't remember if they were there by default or if I copied them there). If the php directory is not in your PATH these latter dll's will not be found and cause the error.
I would suggest checking that the libmysql.dll and/or mysql.dll is in your php directory. If so, add your php directory to your system's PATH and REBOOT your computer. I had the same problem, added the php directory to the system's path, restarted Apache and the problem wasn't solved. I needed to reboot before Apache/PHP would find the dll's in the php directory.
An alternative is to copy libmysql.dll and mysql.dll into a directory that is searched by default (is it the Windows directory or maybe the Window\System32 directory). When the php_pdo_mysql.dll is loaded it will then be able to find the dependent dlls.
If these two dlls aren't in your php directory, try downloading and installing MySQL. You may find these dlls in amongst the files installed my the MySQL installer.
If you're using Apache it should be reporting in the error log that it can't load php_pdo_mysql.dll. If not, maybe it's reporting some other error on start up. Posting any errors from the log maybe helpful for diagnosis.
Hope this helps.