A series of Ag/P-g-C3N4 composites with different Ag content were synthesized for the First time by thermal polymerization combined with photo-deposition method. The composites were characterized by X-ray powder diffraction, field emission scanning electron microscope coupled with energy-dispersive X-ray spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, ultraviolet-visible diffuse reflectance spectra, N-2 absorption-desorption and X-ray photoelectron spectroscopy. Ag was successfully dispersed on the surface of P-g-C3N4. The photocatalytic performance of P-g-C3N4 and Ag/P-g-C3N4 was evaluated by degrading sulfamethoxazole (SMX) under visible light irradiation. In the presence of 5% Ag/P-g-C3N4, 100% of SMX was degraded within 20 min. The enhanced photocatalytic activity of Ag/P-g-C3N4 was attributed to the surface plasmon resonance effect of metallic Ag and Schottky barrier formed on the interface between Ag and P-g-C3N4, which could speed up the generation rate of electrons and holes and inhibit the recombination of photogenerated electron-hole pairs. The radical quenching tests indicated that holes and superoxide radicals were the dominant active species involved in SMX degradation. The synthesized materials maintained high catalytic activity after five cycle runs. The concentration and the intermediates during the degradation process were determined by LC MS/MS, and the tentative degradation pathways of SMX in photocatalytic system were proposed.