It is a promising strategy to effectively promote "carbon neutrality" by reducing CO2 to small energy molecules through photocatalysis technology. However, due to low light utilization and recombination of photogenerated carriers, photocatalysts usually have low activity and low selectivity for products. Herein, a hollow spherical ZnS/ZnO heterojunction with a spatial confinement effect photocatalyst was synthesized toward CO2 photoreduction through preciously controlling the nano-/microstructure. The local lattice distortions were introduced into the surface of the hollow ZnS/ZnO microsphere, which activated lattice oxygen and provided additional active reaction sites. Furthermore, the heterojunction constructed between ZnS and ZnO interfaces facilitated the separation of photoinduced charge carriers. Combined with the natural advantage of enhanced light capture and absorption for a hollow confined structure, as a result, the systemic design in the electronic and confined structures for the photocatalyst has brought an excellent CO2 reduction performance with a CO yield rate as high as 35.85 μmol g–1h–1 and durability under a 300 W Xe lamp irradiation without any sacrificial agent and cocatalyst.