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DExposE2 is a clone of Mac OS X's Expose feature for Windows XP and Vista. Aside from the basic Expose features, DExpose2 features a handful of extra features like interactive previews, hot corners, multi-monitor support, and more.
If you like the look and feel of Expose but have never found a good substitute for your Windows PC, the freeware DExposE2 may be the best available. DExposE2 comes in portable and zipped versions.