The sluggish charge transfer and fast recombination of charge carriers is a determining factor limiting photocatalytic efficiency of carbon nitride. Herein, carbon vacancies and Rh₂O₃ nanoparticles were sequentially introduced into CN to accelerate photo-generated electron and hole transfer simultaneously, thereby improving the photocatalytic performance of CN to achieve the complete removal of Bisphenol A (BPA) in 15 min. Mechanism analyses reveal that the modification of the carbon vacancies regulates the active charge carriers, excitons and trap states, thus enhances the carrier separation capabilities and light absorption. Meanwhile, the in situ photodeposited Rh₂O₃ nanoparticles, as a hole-transfer mediator, maximally suppress recombination of photogenerated charges. These synergistic effects result in promoting the separation and transfer of charge carriers and thus improving photocatalytic performances. This strategy can serve as guideline for the reasonable design of efficient photocatalysts for phenolic wastewater remediation.