Facet-engineered monoclinic scheelite BiVO4 particles decorated with various cocatalysts were successfully synthesized by selective sunlight photodeposition of metal or metal oxy(hydroxide) nanoparticles onto the facets of truncated bipyramidal BiVO4 monoclinic crystals coexposing {010} and {110} facets. X-ray photoelectron spectroscopy, scanning electron microscopy, and scanning Auger microscopy revealed that metallic silver (Ag) and cobalt (oxy)hydroxide (CoOx(OH)y) particles were selectively deposited onto the {010} and {110} facets, respectively, regardless of the cocatalyst amount. By contrast, the nickel (oxy)hydroxide (NiOx(OH)y) photodeposition depends on the nickel precursor amount with an unprecedented selectivity for 0.1 wt % NiOx(OH)y/BiVO4 with a preferential deposition onto the {010} facets and the edges between the {110} facets. Moreover, these noble metal-free heterostructures led to remarkable photocatalytic properties for rhodamine B photodecomposition and sacrificial water oxidation reactions. For instance, 0.2 wt % CoOx(OH)y/BiVO4 led to one of the highest oxygen evolution rates, i.e., 1538 μmol h–1 g–1, ever described which is ten times higher than that found for bare BiVO4. The selective deposition of cobalt (oxy)hydroxide species onto the more electron-deficient facet of truncated bipyramidal monoclinic BiVO4 particles favors photogenerated charge carrier separation and therefore plays a key role for efficient photochemical oxygen evolution.