To realize the evolution of C2+ hydrocarbons like C2H4 from CO2 reduction in photocatalytic systems remains a great challenge, owing to the gap between the relatively lower efficiency of multielectron transfer in photocatalysis and the sluggish kinetics of C-C coupling. Herein, with Cu-doped zeolitic imidazolate framework-8 (ZIF-8) as a precursor, a hybrid photocatalyst (CuOX@p-ZnO) with CuOX uniformly dispersed among polycrystalline ZnO was synthesized. Upon illumination, the catalyst exhibited the ability to reduce CO2 to C2H4 with a 32.9% selectivity, and the evolution rate was 2.7 mu mol.g(-1).h(-1) with water as a hole scavenger and as high as 22.3 mu mol.g(-1).h(-1) in the presence of triethylamine as a sacrificial agent, all of which have rarely been achieved in photocatalytic systems. The X-ray absorption fine structure spectra coupled with in situ FT-IR studies reveal that, in the original catalyst, Cu mainly existed in the form of CuO, while a unique Cu+ surface layer upon the CuO matrix was formed during the photocatalytic reaction, and this surface Cu+ site is the active site to anchor the in situ generated CO and further perform C-C coupling to form C2H4. The C-C coupling intermediate *OC-COH was experimentally identified by in situ FT-IR studies for the first time during photocatalytic CO2 reduction. Moreover, theoretical calculations further showed the critical role of such Cu+ sites in strengthening the binding of *CO and stabilizing the C-C coupling intermediate. This work uncovers a new paradigm to achieve the reduction of CO2 to C2+ hydrocarbons in a photocatalytic system.