Don't forget Java
I'm with ghstdrgns on this one as far as the longevity of both .NET and php. Both have definite advantages and both have their own holds on the market.
That said, if I were beginning to learn web design and development right now and was trying to figure out which one to learn in pursuing a career I would choose .NET. I am a php developer and have been working for just over 3 1/2 years for PlanHouse in Jackson, Mississippi. I am happy doing what I do and would, given a choice, continue to work with PHP. Because of romantic involvements, I am currently seeking new employment in the New England area and I have quickly realized that while my preference is for PHP, most of the web development/application/programming jobs that I am able to find are either .NET or Java.
As .NET and Java currently seem to have a good hold on the web development world as far as those who are hiring in the area I want to live, I have started to work on gaining proficiency in both. In my case, I am more strongly pursuing work with Java because I have some interest in eventually working as a programmer, with the option of going back to web development when necessary.
PHP or .NET? .NET is paying right now, but so is Java and my current thoughts are that Java will give you more options than web development.
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