Through density functional theory (DFT) computations and experimental tests, we investigated the catalytic properties of Sb2S3 crystals with different facets used as counter electrodes (CEs) for dye-sensitized solar cells (DSSCs). The computations show that, compared with the (151) facet, the (211) facet has greater surface activity and better electrical conductivity but markedly lower band-edge levels, resulting in comparable catalytic activities for these two facets. To verify these predictions, we synthesized two Sb2S3 nanowire bundles, predominantly with exposed (151) and (211) facets, and found that DSSCs with these Sb2S3 CEs have similar I–V curves and conversion efficiencies, which confirms the computations and suggests that the surface activity, electrical conductivity, specific surroundings, and band-edge positions should all be considered in the design of semiconductor CEs for DSSCs.