Yes, you can have both VS 2005 and VWD Orcas Express on the same machine ("side-by-side installation"). However, if the only reason you want it is to target different framework versions, then you no longer need to do this. VS 2008 ("Orcas") can target both 2.0 and 3.5 versions of the framework. It's called "multi-targeting". When you are creating a web site, you will be able to choose which framework version you want to target. Please see ScottGu's blog for more info:
http://weblogs.asp.net/scottgu/archive/2007/06/20/vs-2008-multi-targeting-support.aspx
If you decide to go with side-by-side configuration anyway, then read this. With the current (Beta 1) release of VWD Orcas Express, there are some minor issue with side-by-side installation with VS 2005. However, Beta 2 of Orcas will come out shortly, which fixes most of these issues. I am not going to promise there won't be any issues at all, but this is definitely a supported configuration.
This posting is provided "AS IS" with no warranties, and confers no rights.