Porous carbon supported Cu2O/Cu dual-phase catalysts were prepared via a combined solvothermal and sintering method, and their catalytic activities were investigated in catalytic nitrophenol reduction. XRD characterization indicated that the Cu2O/Cu phase can be obtained by sintering Cu-BTC under air atmosphere, whereas Cu phase can be gotten under nitrogen annealing atmosphere. The morphologies of catalysts Cu2O/Cu were checked using SEM and TEM. SEM and TEM images showed that Cu2O/Cu composite catalyst obtained in the nitrogen atmosphere has smaller particle size and higher dispersions than those of CuO catalyst obtained under air atmosphere. In the catalytic nitrophenol reduction, porous carbon supported Cu2O/Cu dual-phase catalysts obtained under nitrogen atmosphere exhibits much higher catalytic activity compared with CuO from air atmosphere.