I have PHP5, Apache2, mySQL 5, PostgreSQL, MS SQL all running in Windows XP Pro x64. It does work.
What you need to do is in your httpd.conf file (Located In: C:\Program Files (x86)\Apache Group\Apache\conf) is add this at the bottom:
LoadModule php5_module "C:/PHP/php5apache2.dll"
PHPIniDir: C:\PHP
This will load the PHP module in Apache, and point Apache to the php.ini file which is needed for Apache to initialize PHP properly.
Then, you also need to add "C:\PHP" to your Path variable. You can do that by:
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Right-click My Computer
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Choose Properties
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Select "Advanced" Tab
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Click "Environment Variables" buttton (bottom area)
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In the bottom group, where it says "System Variables", scroll down and select "Path".
[indent]It should already have a value of something like: "%SystemRoot%\system32;%SystemRoot%;"[/indent]
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Go to the end, and add this: ";C:\PHP"
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Click "Ok", Click "Ok", Click "Ok"
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Restart computer
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Start Apache (if not automatically configured to do so)
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Try and run a PHP script
If that still doesn't work, may I suggest you uninstall everything, and work through this tutorial:
Installing a new web server: Apache2, PHP5, mySQL, phpMyAdmin