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VB.NET is easier to learn, but I would go with C# for most windows based projects. Why not learn it now, instead of later when you realize VB.NET will not quite perform how you want it to?
I suggest PHP for web development. Picking up a bit of database knowledge will do you well also... mysql.com.
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http://jasonpowers.net
"There are a thousand hacking at the branches of evil to one who is striking at the root."
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