A series of barbituric acid doped carbon nitride (CN-BA) photocatalysts were successfully prepared by copolymerizing dicyandiamide with barbituric acid (BA). Under AM1.5 simulated sunlight, CN-BA photocatalysts exhibit enhanced photocatalytic activity compared to pure carbon nitride for the degradation of aniline. The highest activity is obtained with 2% doped CN-BA photocatalyst. Results on the photodegradation of aniline indicate that for the optimized CN-BA photocatalyst, the concentration of aniline solution was reduced gradually from 16 mg/L to 1.354 mg/L in 2 h. This corresponds to a 6 times higher photodegradation efficiency than pure carbon nitride samples. The enhanced photocatalytic activity of CN-BA relies on the enhanced surface area, the higher light absorption and the reduced recombination of the photo-generated electron-hole pairs. This interpretation results from multiple characterizations with EPR, BET, N2adsorption, Solid-state13C NMR, UV–vis DRS, FESEM, and TEM. Under simulated sunlight irradiation, CN-BA is excited and generates electron-hole pairs. The photo-generated electrons in the CN-BA conduction band react with the molecular oxygen to form [rad]O2−. Part of the [rad]O2−transforms into [rad]OH, which further oxides aniline. Meanwhile, photo-generated holes in the valence band of CN-BA can benefit to the formation of [rad]OH or directly oxide aniline.