Multicomponent oxides and their heterostructures are rapidly emerging as promising light absorbers to drive oxidative chem. To fully exploit their functionality, precise tuning of their compn. and structure is crucial. Here, we report a novel soln.-based route to nanostructured bismuth vanadate (BiVO4) that facilitates the assembly of BiVO4/metal oxide (TiO2, WO3, and Al2O3) nanocomposites in which the morphol. of the metal oxide building blocks is finely tailored. The combination of transient absorption spectroscopy-spanning from picoseconds to second time scales-and photoelectrochem. measurements reveals that the achieved structural tunability is key to understanding and directing charge sepn., transport, and efficiency in these complex oxide heterostructured films.