Cycles: Assign material to vertex group I know it's possible to have multiple shaders for one object with the internal renderer. This video explains the process.

Can I use Cycles to assign a material to a vertex group so that a single object may have multiple materials? If so, how?
Yes. It works exactly the same, just press the "Assign" button with the desired vertex-groups/faces selected. Unassigned geometry uses the default (first) material slot.