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I'm not sure this is an XE-specific question. However, there's not much examples outside, probably because it's not a very common solution. I'd say it should work, as PowerPivot offers OLE DB and ODBC connectors and XE comes with appropriate ODBC drivers installed. So, as long as your XE is on the same machine as your PowerPivot, you don't have to care much about that. Otherwhise you'll probably have to install the ODBC driver, e.g. from [url http://www.oracle.com/technetwork/developer-tools/visual-studio/downloads/index.html]Oracle Data Access Components (ODAC).
Then create your ODBC data source, test it, and link it in PowerPivot.