Yes, for a few reasons:
1) .net wraps Win32 code. .net is usually a superior system to code against, but having some knowledge of the underlying Win32 layer (oops, WinAPI now that there is 64-bit code too) bolsters your knowledge of what is really happening.
2) in this economy, it is better to have some advantages over the other guy when you are looking for a job. Some WinAPI experience may provide this for you.
3) some system aspects are not available through the .net framework yet, and if you want to access those features you will need to use p/invoke (see http://www.pinvoke.net for some help there). Having at least a smattering of WinAPI experience will make your p/invoke development effort a lot more efficient.
4) (added) Now that Win8 has been around for awhile, it is still built on top of the WinAPI. iOS, Android, OS/X, and Linux are all out there, but the WinAPI will still be out there for many many years.
