Heterostructured nanomaterials can paid more significant attention in environmental safety for the detection and degradation/removal of hazardous toxic chemicals over a decay. Here, we report the preparation of hierarchically nanostructured shuriken like bismuth vanadate (BiVO4) as a bifunctional catalyst for photocatalytic degradation and electrochemical detection of highly toxic hexavalent chromium (Cr(VI)) using the green deep eutectic solvent reline, which allows morphology control in one of the less energy-intensive routes. The SEM results showed a good dispersion of BiVO4 catalyst and the HR-TEM revealed an average particle size of ca. 5-10 nm. As a result, the BiVO4 exhibited good photocatalytic activity under UV-light about 95% reduction of Cr(VI) to Cr(III) was observed in 160 min. The recyclability of BiVO4 catalyst exhibited an appreciable reusability and stability of the catalyst towards the photocatalytic reduction of Cr(VI). Also, the BiVO4-modified screen printed carbon electrode (BiVO4/SPCE) displayed an excellent electrochemical performance towards the electrochemical detection of Cr(VI). Besides, the BiVO4/SPCE demonstrated tremendous electrocatalytic activity, lower linear range (0.01-264.5 mu M), detection limit (0.0035 mu M) and good storage stability towards the detection of Cr(VI). Importantly, the BiVO4 modified electrode was also found to be a good recovery in water samples for practical applications.