I have done Melboure to Albury via the highlands. My original plan was to goto Albury around Mt Buffalo, but there is 12k's of dirt road just before Buffalo lakes - so we diverted to the Hume HWy near Benalla.
Mansfield to Whitfield is amazing and also taking the first journey towards the Spur is rewarding as well. The trip to Albury took me 5 hours with a stops at Healesville, Marysville (not nessecary but recommended) and Mansfield for lunch.
Depending on what you ride. I recommond sports bikes do this over two days. Your wrists and back will cop a beating on the straight and boring Hwy's. I was fine travelling along the twisties until I got back onto the hwy.
Albury to Holbrook is very boring as well. After that is get a little twisty, but still a burden on the back and wrists with a sportbike.
Good luck and dont forget, Rain gear and Maps.