This study proposes that metastable WO3 exhibits efficient photoconversion of CO2 to ethylene (C2H4). It is found that 1) the metastable hexagonal WO3 (h-WO3) offers a suitable bandgap for CO2 reduction, and its surface oxygen vacancy can enhance the light absorption capability and promote the separation of photogenerated electron-hole pairs, simultaneously; 2) S atoms replace oxygen atoms as the bridges to connect the adjacent W atoms to form W-S-W sites are beneficial to adsorb the *CH2 intermediates. Consequently, the optimized h-WO3 nanorods integrating oxygen vacancy and sulfur doping together have achieved the C2H4 generation yield of 1121.39 μmol g−1 with the record-high yield-based selectivity of 87.6% and electron-based selectivity of 95.7% in the field of photocatalytic CO2 reduction so far. This work provides a new avenue for the realization of CO2 photoconversion to C2+ products on a single metal oxide by virtue of O vacancy and S doping synergistic utilization.