A Bi2O3/(BiO)2CO3 (BO/BOC) composite photocatalyst was in situ prepared via calcinating (BiO)2CO3. The as-prepared Bi2O3/(BiO)2CO3 composites displayed enhanced photocatalytic activity for the degradation of RhB under visible light. The structure–activity relationship between catalyst structure and properties was investigated by SEM, XRD, XPS, FTIR, BET, DRS and photoelectrochemical tests. Apart from the increased absorption of visible light, the accelerated charge separation and transfer was achieved via the intimate contact and matched band structure between Bi2O3 and (BiO)2CO3. The formation of heterogeneous structures could promote the production of reactive oxygen species (·O2−) and eventually improve the photocatalytic performance for the removal of organic contaminants. This heating treatment strategy might be extended for improving light absorbance and charge carriers separation for other UV-based photocatalysts.