Abstract Phase effect of bismuth vanadate (BiVO4) nanostructured catalysts for the photoelectrochemical (PEC) solar water oxidation, removal of toxic organic pollutants from wastewater, and electrochemical storage were reported. The monoclinic (BV-M) and tetragonal (BV-T) crystal structured BiVO4 photocatalysts were synthesized using a facile hydrothermal route without the support of any template. The BV-T photoelectrode also exhibits lower charge transfer resistance compare to BV-M photoelectrode. The BV-T photoelectrode showed a remarkable photocurrent density (0.4249 mAcm−2) over BV-M photoelectrode (0.0702 mAcm−2), which is about 6 times greater than BV-M photoanode. Furthermore, BV-T sample showed 17 times superior electrochemical capacitance over BV-M sample at the scan rate of 10 mVs−1. The photocatalytic analysis has also shown that the BV-T photocatalyst revealed greater photocatalytic activity for the methyl orange under visible light, about 87.8% of the MO was degraded within 80 min.