Controlling the phase, crystallinity, and microstructure and fabricating a facet isotype heterojunction with a proscribed reduction− oxidation facet exposure factor have a strong constructive effect toward photoexciton separation and migration. In this respect, here diverse synthetic courses such as calcination (BiVO 4 -C), hydrothermal treatment (BiVO 4 -H), and a reflux method (BiVO 4 -R) are introduced to fabricate various hierarchical morphologies of highly crystalline monoclinic scheelite bismuth vanadate (BiVO 4 ) with different redox facet exposure factors that have been well established by X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy analysis. The analytical and experimental investigations revealed superior photocatalytic upshots of a BiVO 4 -R {040/110} facet isotype heterojunction toward levofloxacin (LVF) detoxification (71.2%, 120 min) and the water oxidation reaction (530.6 μmol, 120 min) relative to BiVO 4 -C (42.3%, 434.2 μmol) and BiVO 4 -H (60.4%, 494.8 μmol). Accordingly, the BiVO 4 -R {040/110} facet isotype heterojunction (145.6 μA/cm 2 ) expressed an enhanced photocurrent in comparison to pristine BiVO 4 -C (75.5 μA/cm 2 ) and BiVO 4 -H (113.1 μA/cm 2 ). The superior photocatalytic redox efficiency was attributed to well-exposed {040} reduction and {110} oxidation facets and a superior relative {040} facet exposure factor provoking an enhanced charge carrier separation over a BiVO 4 -R {040/110} facet isotype heterojunction. The spatial exciton separation over the BiVO 4 -R sample was well established by numerous analytical and experimental investigations. The effectual associations among physicochemical, photoelectrochemical properties, {040/110} facet isotype heterojunction, relative reduction−oxidation facet exposure factor, and photocatalytic performances of fabricated BiVO 4 microstructures were well established, and the upshots of this research were discussed finely. The research signifies an effectual direction for morphology and relative reduction−oxidation facet exposure factor controlled fabrication of facet isotype heterojunction based materials for superior photocatalysis and could be advantageous for supplementary research areas.