Platinum (Pt) nanoparticles/nanoclusters are some of the most efficient cocatalysts for photocatalytic CO2 reduction. Nevertheless, the produced CO can lead to a poisoning effect due to the strong adsorption strength of the Pt cocatalysts. Using density functional theory, PtOx clusters with variable sizes (Pt4O6, Pt5O8, Pt7O10, and Pt8O13) are selected to load on WS2 (PtOx-WS2) for photocatalytic CO2 conversion. The calculated results demonstrate that PtOx-WS2 are highly stable, and the electron-rich PtOx clusters are beneficial for the photocatalytic CO2 reduction. All the PtOx-WS2 catalysts exhibit efficient photocatalytic performance for CO2 reduction. Especially, Pt4O6-, Pt5O8-, and Pt8O13-WS2 have acceptable or ultra-low ΔGmax (ΔG for the rate-determining step) of 0.57, 0.23, and 0.48 eV to produce CH3OH, HCOOH, and CH4, respectively. The photocatalytic activities of PtOx-WS2 are correlated with the adsorption strength of the key intermediates, and the strong interactions between PtOx-WS2 and *COOH or *HCOO can lower the free energy changes for the first hydrogenation step. More importantly, PtOx-WS2 can also weaken the adsorption strength of *CO and *HCOOH, which are conducive to forming *CHO. This work gives an in-depth insight to design novel catalysts and promote their catalytic activity for photocatalytic CO2 reduction.