The photoreduction of CO2 to formate (HCOO–) in sphalerite (ZnS) aqueous suspensions is systematically studied in the presence of Na2S hole scavenger. A series of cut-on filters at λcut-on ≥ 280, 295, 305, 320, and 400 nm are used to measure the reaction rate of formate production. The dependence of the measured reaction rates on λcut-on indicates that a wavelength of λ = 345 nm is associated with the actual bandgap of the semiconductor nanocrystallites suspended in water. The results from apparent quantum yield measurements during periodic illumination experiments suggest that (1) valence-band holes on the surface of ZnS disappear within deciseconds due to the oxidation of the scavenger while simultaneously pumping electrons to the conduction band, (2) excited electrons in the conduction band of ZnS are transferred to CO2 to produce the intermediate CO2•–, and (3) CO2•– abstracts a proton from water and undergoes further photoreduction on the surface of ZnS in an overall time scale for steps 2 + 3 of a few milliseconds. The separation of both process merges at 29 ms because it decreases exponentially with a drop in [Na2S] accompanied by a less negative surface potential. The behavior of the reaction rate at variable pH resembles the fraction of dissolved CO2, discarding the direct participation of bicarbonate and carbonate in the reaction. Combined chromatographic, mass spectrometry, and spectroscopic studies provide new insights to understand the role of surface chemistry on the photoreduction of CO2 on ZnS nanocrystals.