What charset does Microsoft Excel use when saving files?

The correct answer to this question lies in a comment of the most popular answer:
The "Web Options" does not apply to CSV exports (at least with Excel 2007). The encoding of the CSV file seems to follow default encoding of the installation. So it can be anything, in practice. Sadly, there does not seem to be a way to control this at export-time.

So if you have to export a CSV from Office 2007 with a specific encoding, then go to "Start Menu / Control Panel / Regional and Language Options / Advanced" and set the "Language for non-Unicode programs" to a language that uses the character set of your choice. Eg. to save CSV files with an ISO-8859-2 (Central European, single byte) characterset, you could choose "Hungarian" for the lang. for non-Unicode programs.

This is pretty annoying if you work with various encodings (since changing the "Language for non-Unicode programs" settings requires a restart ... at least on Windows XP), but that's what you got. Or you can start using OpenOffice/LibreOffice where the encoding handling of files is a lot more easier.