Here, we show the results of a molecular-defined conjugated ketone catalyzed alcohol amination reaction. Under the optimized reaction conditions, the yields to the desired products reached 98%. The reaction mechanism and kinetic study supposed that carbonyl–hydroxyl groups are the catalytically active sites, and the transfer-hydrogenation reactions progress via the recycling of carbonyl and hydroxyl groups. The catalytic process shows promise as an efficient and economic route for alcohol amination reactions.