It is highly desirable to develop efficient heterogeneous photocatalysts for organic reactions. Here, we show the preparation and catalytic performance of a novel TiO₂ (P25) supported Cu and Mo photocatalyst (Cu–Mo/TiO₂) for N-alkylation of amines with alcohols under UV irradiation at room temperature. A variety of aromatic and aliphatic amines were selectively converted into the corresponding secondary amines or tertiary amines in moderate to excellent yields without the addition of any co-catalysts such as bases and organic ligands. Noteworthy, this catalytic system is feasible in the alkylation of anilines containing halogen substituents with alcohols and the yields of the desired products are up to 95%.