The synthesis of heterogeneous metal ligand catalysts with high activity and good recyclability is always an important topic but still challenging to make. Herein, we reported a solid Schiff base Cu catalyst synthesized by incorporating Cu sites into the copolymeric Schiff base ligand, which is achieved from a porous polydivinylbenzene functionalized with Schiff base groups. A heterogeneous Schiff base Cu catalyst denoted as hetero-SchCu was obtained. Systemic characterizations involving XPS, FTIR, N-2 sorption, and electronic microscopy demonstrate the structural features of hetero-SchCu including functionalized Schiff base ligand, stabilized and highly dispersed Cu species, and rich porosity. The hetero-SchCu exhibits high catalytic activity and selectivity in the oxidation of a series of alcohols and cyclohexane. Importantly, the hetero-SchCu is stable and recyclable in the tests involving several runs without a decrease in activity. This work not only demonstrates a platform for developing polymeric heterogeneous catalysts, but also provides efficient catalysts for the oxidation of alcohols and cyclohexane.