Photocatalytic membrane reactors (PMRs) have been widely used in wastewater treatment over the past few years. In this study, P-doped g-C3N4 (PCN), a metal-free, visible light (Vis)-driven photocatalyst, was prepared and coated on an Al2O3 substrate followed by integration with an inorganic Al2O3 hollow fiber membrane module for use as a PMR. The 10 wt % of PCN exhibited the highest degradation activity for methyl blue (MB) removal under Vis irradiation because the C sites and vacancies within the heptazine rings of the CN units were substituted with P to improve charge separation and reduce the number of unpaired electrons. The PMR exhibits higher efficiency and stability in the removal of MB, methyl orange, phenol solution, and a mixture of the three organic compounds than do individual hollow fiber membranes or photocatalysis systems. The TOC (total organic carbon) analysis revealed that more than 92% of the phenol was decomposed and mineralized in the PMR, which also had a MB removal efficiency of greater than 90% when repeatedly used for four times. These results indicate that the PMR developed in this study is highly active and stable, and can serve as a promising system for effective removal of organic pollutants in wastewater. Photocatalytic membrane reactor integrated with P-doped g-C3N4 with Al2O3 hollow fiber membrane module exhibits excellent photocatalytic activity. Display omitted •P replaces C in g-C3N4 structure to improve charge separation and photocatalysis.•P-doped g-C3N4 was fabricated and integrated with photocatalytic membrane reactor.•PMR can be used for wastewater treatment under irradiation of simulated sunlight.•PMR degrades MB under irradiation with light of wavelength larger than 400 nm.