Cu-based catalysts have been shown to selectively catalyze CO2 photoreduction to C2+ solar fuels. However, they still suffer from poor activity and low selectivity. Herein, we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N2 motif (Cu-N2-V). Lead many recently reported photocatalysts and its Cu-N3 and Cu-N4 counterparts, Cu-N2-V exhibits superior photocatalytic activity for CO2 reduction to ethanol and delivers 69.8 μmol g-1 h-1 ethanol production rate, 97.8 % electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N3 and Cu-N4. Revealed by the extensive experimental investigation combined with DFT calculations, the superior photoactivity of Cu-N2-V stems from its defected Cu-N2 configuration, in which the Cu sites are electron enriched and enhance electron delocalization. Importantly, Cu in Cu-N2-V exist in both Cu+ and Cu2+ valence states, although predominantly as Cu+. The Cu+ sites support the CO2 activation, while the co-existence of Cu+/Cu2+ sites are highly conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C-C coupling. Furthermore, the hollow microstructure of the catalyst also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N2-V an effective and high-performance catalyst for the solar-driven CO2 conversion to ethanol. This study also elucidates the C-C coupling reaction path via *CO-*CO to *COCOH and rate-determining step, and reveals the valence state change of partial Cu species from Cu+ to Cu2+ in Cu-N2-V during CO2 photoreduction reaction.