If you have the libraries needed add the --with-pspell[=dir] option when compiling PHP.
Note: Note to Win32 Users
In order for this extension to work, there are DLL files that must be available to the Windows system PATH. For information on how to do this, see the FAQ entitled "How do I add my PHP directory to the PATH on Windows". Although copying DLL files from the PHP folder into the Windows system directory also works (because the system directory is by default in the system's PATH), this is not recommended. This extension requires the following files to be in the PATH: aspell-15.dll from the bin folder of the aspell installation.
Win32 support is available only in PHP 4.3.3 and later versions. Also, at least aspell version 0.50 is required.