At room temperature, SO42-/TiO2 and SO42-/nano-TiO2 efficiently catalyze the direct Mannich-type reaction of varieties of in situ-generated aldimines using aldehydes and anilines with ketones in a three-component reaction under solvent-free conditions. The reaction proceeds rapidly and affords the corresponding beta-amino ketones in good to high yields with good to excellent stereoselectivity. The catalyst can be recycled for subsequent reactions without any appreciable loss of efficiency.