A metal-free modified carbon nitride MCU(DMSO)-CN (3:3:1) with a honeycomb-like morphology was prepared via firstly introducing cyanuric acid and urea into melamine in dimethyl sulfoxide (DMSO) as the precursor for the MCU-CN. A variety of characterization methods, including XRD, XPS, FT-IR, SEM, TEM, UV-vis, photoluminescence (PL), and photocurrent generation, were applied to investigate the structure, morphology, optical, and photoelectrochemical properties of the g-CN and MCU-CN (3:3:1). Rhodamine B (RhB), methylene blue (MB), and bisphenol A (BPA) were selected as target pollutants to evaluate photocatalytic activity of the MCU-CN (3:3:1) under visible light irradiation. MCU-CN (3:3:1) exhibits significantly enhanced photocatalytic activity compared with g-CN, where 99.49% RhB is removed within 40min, 97.7% MB is removed within 80 min, and 84.37% BPA is removed within 90 min. The improved photodegradation efficiency was mainly due to the larger surface area, the stronger REDOX ability, and the increased separation efficiency of photogenerated electron-hole pairs. The active radical trapping experiments and electron spin resonance tests indicated that h and O radicals were the dominant active species whereas OH radicals could be a minor factor. A possible photocatalytic mechanism is proposed. This strategy here provides an ideal platform for the design of photocatalysts with large surface area and high porosity for various pollutant controlling applications.