Semiconductor-based artificial photoredox-catalyzed organic synthesis offers a promising and green opportunity to harness solar energy for green organic chemistry. However, the precise manipulation of product selectivity over semiconductor-based photocatalysts for selective organic synthesis remains challenging. In this work, we report the rational preparation and application of two kinds of cocatalyst, (RuS₂ or Cu₂S)-decorated monolayer ZnIn₂S₄, for the selective dehydrocoupling of aromatic amines into tunable CN coupled imines or C–N coupled secondary amines, respectively, under visible light irradiation. The presence of the RuS₂ or Cu₂S cocatalyst not only facilitates the charge carrier separation and migration owing to the well-matched energy band structure, but also maneuvers the interfacial charge transfer routes for the selectivity switching between CN and C–N product formation. This work would inspire the rational design of ingenious semiconductor-based composites toward selective modulation in heterogeneous photocatalytic organic synthesis.