Phosphorus doped graphitic carbon nitride (g-C3N4) was easily synthesized using ammonium hexafluorophosphate (NH4PF6) as phosphorus source, and ammonium thiocyanate (NH4SCN) as g-C3N4 precutsor, through a direct thermal co-polycondensation procedure. The obtained phosphorus doped g-C3N4 was characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectra (FTIR), UV-vis diffuse reflectance absorption spectra (UV-DRS), photoelectrochemical measurement and photoluminescence spectra (PL). The photocatalytic activities of phosphorus doped g-C3N4 samples were evaluated by degradation of Rhodamine B (RhB) solution under visible light irradiation. The results showed that the phosphorus doped g-C3N4 had a superior photocatalytic activity than that of pristine g-C3N4, attributing to the phosphorus atoms substituting carbon atoms of g-C3N4 frameworks to result in light harvesting enhancement and delocalized IT-conjugated system of this copolymer, beneficial for the increase of photocatalytic performance. The photoelectrochemical measurements also verified that the charge carrier separation efficiency was promoted by phosphorus doping g-C3N4. Moreover, the tests of radical scavengers demonstrated that the holes (h(+)) and superoxide radicals (O-center dot(2)-) were the main active species for the degradation of RhB. (C) 2016 Elsevier B.V. All rights reserved.