No, it is not available on the app store. You would have to obtain an older version of iLife to get iWeb. Check out Amazon if you really want it. Honestly, even though I really loved iWeb for its simplicity, you should probably go with something more modern. There are several apps out there that basically take the place of iWeb and you could also easily learn WordPress. At least with WordPress you're not tied to a platform and can even do updates from mobile devices.
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Edit:
For a direct replacement to the iWeb app you might look at these:
http://www.karelia.com/products/sandvox/
http://www.everwebapp.com/
For a direct replacement to the iWeb app you might look at these:
http://www.karelia.com/products/sandvox/
http://www.everwebapp.com/
Download Iwebtv For Mac Osx
Or if you don't feel like messing with WordPress and want something that isn't tied to the Mac platform you could get the basic equivalent from services like these:
http://www.squarespace.com/
http://www.wix.com/
http://www.squarespace.com/
http://www.wix.com/