 The development of efficient and stable electrode materials is a cutting-edge method to improve electrocatalytic activity. The way of combination biomass-derived porous carbon and metal oxides is considered to be an effective strategy to improve the redox reaction. In this study, we selected tea as a biomass carbon source and synthesized 3D structure of tea porous carbon (TPC) using a template-free method. TiO2/TPC composite material was successfully prepared through one-step simple hydrothermal reaction without destroying the pore structure. The degradation effect of phenol and the yield of ·OH were used as the evaluation criteria for the electrocatalytic performance of composites. The results show that TiO2/TPC-1:2 (20) has an excellent phenol degradation effect (97.54%). The good degradation effect is based on the reasonable design of the structure of composite materials. This effective preparation strategy of composite maximizes the advantages of the pore structure of the material itself and creates a large number of good channels for electron transport. At the same time, the load of metal oxide can effectively promote more catalytic active sites, which has a certain significance for the preparation of porous carbon or porous carbon matrix composite materials.