There are differences between the two, with relation to:
- Generics
- Optional Parameters (this changes in 4.0)
- Catch/When clauses
with
in VB
- named/unnamed indexers
- etc...
That being said, they're 99.9% the same, just a matter of syntax. I started with VB.Net because it was a project in my first Co-Op, since then I switch to C# years ago and found it to be much easier...it's a matter of taste but not a big deal to switch. It's the framework you're using, the language is just a nuance, it's all IL in the end.
The things you can do in one language and not the other are usually trivial, and you're getting very advanced if it's something you can't work around. The .Net team does a very good job of keeping the languages and their capabilities in sync these days (this started about a year ago when it was time for LINQ, many more differences existed before then).