Good Day Sudhir
The Best way to learn is to buy a Book. But here are the Reference materials that you can use to get your self started
WCF
http://msdn.microsoft.com/en-us/library/aa480190.aspx
http://msdn.microsoft.com/en-us/magazine/cc700338.aspx
http://www.codeproject.com/KB/webservices/Programming_WCF.aspx
http://www.c-sharpcorner.com/UploadFile/john_charles/Introduction_to_Windows_Communication_Foundation11062006143953PM/Introduction_to_Windows_Communication_Foundation.aspx
Web Services
http://www.w3schools.com/webservices/ws_intro.asp
http://www.developer.com/services/article.php/1485821/Introduction-to-Web-Services.htm
http://www.codeproject.com/KB/IP/intro2websvc.aspx
Thank you for posting at DotnetFunda
Vuyiswa Maseko