Skype provides a COM API that can be used from VB.NET. For more info on using COM from VB.NET see:
http://msdn.microsoft.com/en-us/library/x66s8zcd.aspx
The Skype API documentation can be found at:
https://developer.skype.com/Docs/ApiDoc
And, although not in VB.NET there is good example of how to use the Skype API in the SEHE AKA Skype Event Handler Example. It is written in C#, but the same principles apply to VB.NET, just slightly different syntax.
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