Andy Beynon, 52, from Llanelli, Carmarthenshire, died on the B4268 between Pentre Meyrick Cross and Llysworney.
His wife said he was the "love of my life" who dedicated his time to helping children with special needs.
The crash involved Mr Beynon's motorbike and a Land Rover Freelander.
In a statement, his wife Dawn said: "Andy lost his life enjoying one of his many pleasures - riding his motorcycle.
"He was out that day giving his free time to teach others how to become a better rider.
"He was a loving husband, father, grandfather, brother - a family man - with many, many friends.
"He dedicated his time to help others and work tirelessly helping children with exceptional special needs. The children utterly adored him - he just had that 'special gift' to make them smile."
A motorcyclist killed in a crash in the Vale of Glamorgan on Saturday has been described as "the love of my life" by his wife.