Download the ICO Format Photoshop Plugin and install it in the Photoshop Plugins folder.
Applications\Adobe Photoshop CS5\Plug-ins\File Formats\ICOFormat.plugin
C:\Program Files\Adobe\Adobe Photoshop CS5 (64 Bit)\Plug-ins\File Formats\ICOFormat64.8bi
You can use .gif files, but IE won’t show them…only .ICO’s are compatible to most browsers.
http://www.telegraphics.com.au/svn/icoformat/trunk/dist/README.html