You don't have to use XML in .NET, depends on what you're doing. I'm interested to hear what you think XML is- it's not a language like VB, it's just a way to hold information in a file. Have you used CSV files before? XML is basically a fancy CSV file.
Yes, .NET has some great APIs to help you read in and manipulate these XML files, but you can do a lot without XML too.
However, you shouldn't just ignore XML- even with a basic understand of XML structure, it is still very powerful when used in the right places.
XML isn't the answer to everything though.