I suppose it depends on the industry and market you are looking in. For me, I see a lot of demand for PHP, DotNet (usually C#/ASP.NET though also VB, not that there is a lot of difference between the two IMHO).
I haven't seen much in the way of Python or Java for that matter, unless its J2EE. Having said that, they are both good and flexible languages, and I feel that the more exposure to different technologies you have experienced is better for your development as a programmer in general.
You will find that a good knowledge of web standards CSS, HTML and javascript will help regardless of what backend language is being used. More and more systems programming is becomming web based rather than client side applications, with more companies converting legacy systems into intranets and the like.
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