The photodeposition of Pt nanoparticles from [PtCl6]2− on platelike WO3 crystals occurs preferentially on the small, subordinate facets. Rather than the often‐used explanation of preferred light‐induced charge migration, we propose that this phenomenon is due to differences in the intrinsic surface charges of WO3 facets exposed to water; thus, the dark sorption of [PtCl6]2− on positively charged facets/edges is preferred. This conclusion is based on 1) (dark) impregnation studies, which showed Pt deposition to also be facet‐specific, and 2) aqueous‐phase AFM studies, which suggest intrinsic surface charges to be in agreement with sorption‐based Pt distributions.