Bismuth sphere doped g-C3N4 (Bi/C3N4) nanohybrid has been prepared via a two-step solvothermal method successfully. The structures, morphologies and optical properties of photocatalysts were explored by XRD, SEM, TEM, EDS, XPS and UV-vis spectra. Photocatalytic activities were measured by hydrogen evolution from antibiotic wastewater based on an inspiration of waste to energy. The optimal 2%Bi/g-C3N4 samples demonstrated a H-2 evolution rate of 35.9 mu mol/h under visible light, which was approximately three times that of pure g-C3N4. Further exploration revealed that hydrogen generation can be enhanced by the Surface Plasmon Resonance (SPR) effect of metallic bismuth, which can be verified by photoluminescence spectra (PL) and time-resoled photoluminescence decay analysis. The products were investigated by gas chromatography (GC) and high performance liquid chromatography (HPLC). Results confirmed that hydrogen evolution with simultaneous degradation of antibiotic wastewater can be achieved. The photocatalytic reaction pathway was determined using the high performance liquid chromatography-mass spectrometer (HPLC-MS) technique, either. Moreover, the samples performed good stability during cycling experiments after studied by XRD and XPS characterizations.