Fundamental fact: Learning XML offline does not make sense since XML is not used offline.
Since you are going to learn WCF, I would suggest you get WebServices first. This way you will learn the basics you want to learn about XML, as well as its relevance as a choice for serialized data transfer.
It would also be useful to learn about the various benefits and support options for SQL Server for XML.
So, learn XML in conjunction with the appropriate technology, which will be more useful to you.
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