If you want to modify the actual Office software, you are out of luck. Office is a proprietary product. It is not open source. It is owned by Microsoft, who do not publish the source code.
That said, there are many of ways of customising and extending the Office software. There are dozens of settings you can change. And in the case of Word and Excel (UPDATE: and PowerPoint), you can write macros to extend its functionality.
If you would care to tell us what mods you have in mind, we can provide more specific information.
Regarding XML, Office uses XML as the basis for its document file format. You asked if it uses "XML for programming". I'm not sure what that means, but I suspect the answer is no.
Mike
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Mike Lewis (Edinburgh, Scotland)
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