AbstractThe great demand for visible‐light‐induced catalysts with high photocatalytic performance has stimulated extensive interest in constructing g‐C3N4‐based Z‐Scheme heterojunctions. In this research work, the g‐C3N4/Bi2O3 Z‐Scheme heterojunction by precipitation‐hydrothermal method was constructed, and characterized by various techniques. The g‐C3N4/Bi2O3‐1 composite exhibited a transient photocurrent response approximately 7 and 5 times higher than that of bare g‐C3N4 and Bi2O3, respectively, and showed higher visible photocatalytic activity with 99.8 % degradation of methylene blue (MB) within 75 min. Meanwhile, the pH effect on the photocatalytic degradation of MB was investigated. Radicals trapping experiments showed that •OH free radical played a predominant role for the degradation of MB, EPR analysis confirmed the presence of superoxide radicals, which combined with the band structure of the composites, confirmed the Z‐Scheme of the heterojunction. A possible mechanism for photocatalytic degradation of MB dyes in g‐C3N4/Bi2O3‐1 composites was also proposed. This study provided a new avenue for the development of novel g‐C3N4‐based Z‐Scheme heterojunction materials with prospective applications in the fields of energy and environment.