There is not yet a free demo, but there is something just about as good. There is a $25 modo training pack that has a set of introductory videos walking you through virtually every aspect of modo. With the training material you get a demo of modo 301. So, for $25 you get the training material and 30 day demo that is fully functional (including saving/exporting models of any polygon count). You are NOT paying for the demo (it is free), but for the training material.
While Luxology is not directly supporting Vista yet, the program runs perfectly well on both 32-bit and 64-bit Windows Vista editions. I am run my copy of modo on Windows Vista Ultimate (32-bit) and have no problems. The thing that can cause modo the most problems is which video card you have and this is mainly dependent on which driver you have installed.
Modo and Blender are similar in that they both are modeling programs with a lot of features. In one way Blender is ahead of modo in that it allows for full animation. Modo currently only allows for key frame animation. However, character animation is planned for future releases. Modo is a new tool that was originally released as a modeling-only app and has, since its initial release, grown to include advanced rendering, 3D painting, advanced UV mapping, sculpting and not basic animation.
In my opinion, modo is way more of an advanced modeler than Blender is. Modo is truly a professional tool and this is reflected in the price. This is not to say that Blender cannot be used professionally. It certainly can. However, I simply find that I can do A LOT more in modo and do it A LOT more QUICKLY and, more importantly, A LOT more EASILY.