I've been too busy implementing SpreadsheetML in PHP, that I completely forgot to write something on OpenXML and C# on my blog. Luckily, Joris did now: Generating Office 2007 documents in C#. Now learn some PHP too, Joris, I can use a hand on PHPExcel [:P]
Here are some additional links to get you started:
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OpenXML ECMA specifications (the complete OpenXML specs, a HUGE set of documents explaining almost everything)
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OpenXML explained (Wouter's book on OpenXML, actually the basics of the ECMA specs you will be confronted with while developing)
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OpenXMLdeveloper.org (forums, how-to's, ...)
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PackageExplorer (Wouter's way to validate your OpenXML document, and browse trough all parts inside an OpenXML package - it also includes a cool start page created by a Belgian developer [<:o)])
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Microsoft Office2007 compatibility pack for OfficeXP and Office 2003
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Videos of the worldwide OpenXML workshops by Doug and several others
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Brian Jones' blog, Office rogram manager
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A small Wordpad-alike C# project spitting out WordML, source code included!
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My own blog posts [Y]