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Non-noble metal for surface plasmon resonance (SPR)-induced nano-enzymatic photoelectrochemical (PEC) biosensors is a promising method for broad applications. Non-noble metal bismuth (Bi) is gradually being valued for their properties such as non-toxicity, abundant reserves, and good catalysis. Meanwhile, metallic Bi nanoparticles (NPs) have superior SPR properties similar to that of noble metal. Therefore, a non-noble metal Bi/BiVO4 photoanode based on SPR was designed for the PEC detection of H2O2 in this work. The synergistic effect of BiVO4 with suitable band gap (2.5 eV) and Bi NPs with superior SPR effectively reduces the recombination of photogenerated electrons and holes, which significantly improves the PEC activity of Bi/BiVO4 electrode at low voltage. The in situ Bi/BiVO4/FTO photoelectrode not only exhibits a more comprehensive linear range of 0.005–2.6 mM with a lower detection limit of 2.0 μM but also possesses excellent selectivity for the determination of H2O2 because the coexisting substances are difficult to be oxidized at 0 V bias voltage. The investigation of Bi/BiVO4-based sensor has contributed to the development of non-noble metal for SPR-induced PEC biosensors. [ABSTRACT FROM AUTHOR]