Properly Rigging in Blender without Weight Painting?

At first weight painting was pretty cool, but I noticed it started to not get like like 20% of the vertices and required me to keep painting and going inside the model on more complex models.

Is there another way to rig, I recall seeing a tutorial where you could select certain faces and assign a particular bone to it, that would make things much easier.

I’m using Blender 2.63