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Try this:
1. Right-click on any Mobi book, and choose Open With, then Choose Program.
2. In the resulting dialogue, choose the application that you want to use to read the book (such as Mobi Reader).
3. Tick the box labelled "Always use the selected program to open this kind of file".
4. Click OK.
From now own, simply double-clicking on a Mobi file will open it in your preferred application.
If, in step 2, you can't see the application in the list of programs, click the Browse button, and navigate to the program in question.
Note that the above applies to Windows XP. The steps might be slightly different in other versions, but the overall approach should be the same.
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