To provide a solution for pursuing high redox reactivity beyond the compromise between the numbers of sulfur vacancies and electron transfer ability, 2D-2D architecture of MoS2/rGO composite was fabricated with 2D graphene-like transition metal dichalcogenides and graphene. By employing this material as heterogeneous catalyst, imines, also known as Schiff base, was synthesized by direct aerobic oxidative coupling of amines. Taking advantage of few-layered MoS2 nanosheets and graphene, catalytic performance was significantly enhanced, exhibiting both excellent conversion and remarkable selectivity. Due to the good oil-absorbing capability of this open porous 2D-2D architecture, the hydrolysis of NH-imines by water was inhibited and thus aldehydes byproducts were diminished. A second order kinetic behavior was observed in the imines formation, indicating the bimolecular condensation might be the rate determining step in such coupling reaction.