The fun part is, I do have .NET 4.0 installed, as well as all GTK#. I thought maybe I installed it in the wrong order or something ridiculous, so I uninstalled and re-installed everything. I even tried installing plain old mono, and then installing monodevelop, but I still get that same error.
IIRC MonoDevelop 2.4 had a bug that prevented it targeting the final released version of .NET 4.0. The fix should be in MonoDevelop 2.4.1.
As a workaround, assuming you installed Mono 2.8 (which has 4.0 support), you can change your target runtime to Mono instead of .NET. Either
or