Solar-driven CO 2 conversion to multicarbon (C 2+ ) products has emerged as a key challenge, yet this calls for a systematic investigation on the overall reaction process and mechanism at an atomic level based on the rational design of highly selective photocatalysts. Herein, we report the synthesis of compact Bi 2 S 3 /CdS heterostructures via facile cation exchange, by which a unique pathway of CO 2 -to-C 2 H 4 photoconversion is achieved. Specifically, the BCS-30 shows an optimal C 2 H 4 production rate of 3.49 μ mol h -1 g -1 based on the regulation of band structures and energy levels of photocatalysts by controlled growth of Bi 2 S 3 at CdS surface. Both experimental and theoretical results (DFT calculations) identify Bi atoms as new catalytic sites for the adsorption of CO * and formation of * CO- * CO dimers that further hydrogenate to produce ethylene. Overall, this work demonstrates vast potentials of delicately designed heterostructures for CO 2 conversion towards C 2+ products under mild photocatalytic conditions.