I'd rather hire someone the is programming C# than VB.Net for some reasons I've experienced:
1) Professional/advanced programmers tend to choose C# because of it's syntax.
2) C# programmer most often have background from other programming languages.
3) Every C# programmer I've met reads and writes VB.Net code very good, while VB.Net programmers scratch their head and give up when they see a few lines of C# code.
4) Beginners tend to start with VB.Net. While other programmers start with C# when moving to the .Net platform. Also I've seen many moving from VB.Net to C# after some time. I have never seen anyone move from C# to VB.Net (unless "forced" by management).
This is only what I've seen, and ofcourse isn't the most important aspect of hiring someone for a job.
(I'm programming both C# and VB.Net