Suzuki coupling reaction is a widely practiced protocol in organic synthesis for the formation of C–C bonds. The conventional process for this reaction usually involves high temperatures and noble metals. Hence, the development of a green, cost-effective photocatalytic system is an attractive and challenging strategy for the reaction. Here, we report a modified palladium-free Co-doped BiOCl/Ce-doped Bi2O2CO3 (CBCB) composite, which shows high photocatalytic activity under white LED irradiation. At room temperature, an excellent yield (91%) of the desired cross-coupling product biphenyl was obtained in environmentally friendly solvents. Density functional calculations, together with the experimental results, show that the presence of Co and Ce ions results in the appearance of some impurity levels near the Fermi level of pure BiOCl and Bi2O2CO3, which decreases their forbidden bandwidth, thus ensuring higher light absorption and superior electronic conductivity. Moreover, the intimate interfacial contact between Co-doped BiOCl and Ce-doped Bi2O2CO3 planes has a significant impact on the separation and transfer of photoinduced charge carriers, which ultimately leads to a remarkable increase in visible-light-driven photocatalytic activity.