I had the similar issue. I solved it the following way after a number of attempts to follow the pieces of advice in the forums. I am reposting the solution because it could be helpful for others.
I am running Windows 7 (Apache 2.2 & PHP 5.2.17 & MySQL 5.0.51a), the syntax in the file "httpd.conf" (C:\Program Files (x86)\Apache Software Foundation\Apache2.2\conf\httpd.conf) was sensitive to slashes. You can check if "php.ini" is read from the right directory. Just type in your browser "localhost/index.php". The code of index.php is the following:
<?php
echo phpinfo();
?>
There is the row (not far from the top) called "Loaded Configuration File". So, if there is nothing added, then the problem could be that your "php.ini" is not read, even you uncommented (extension=php_mysql.dll and extension=php_mysqli.dll). So, in order to make it work I did the following step. I needed to change from
PHPIniDir 'c:\PHP\'
to
PHPIniDir 'c:\PHP'
Pay the attention that the last slash disturbed everything!
Now the row "Loaded Configuration File" gets "C:\PHP\php.ini" after refreshing "localhost/index.php" (before I restarted Apache2.2) as well as mysql block is there. MySQL and PHP are working together!