In this study, a non‐enzymatic hydrogen peroxide photoelectrochemical (PEC) sensor based on nanoporous BiVO4 film electrode is fabricated by electrodeposit of nanoporous BiOI film on fluorine‐doped tin oxide glass (FTO) and subsequent conversion to BiVO4 by annealing at elevated temperature. The electrode exhibits excellent visible light photoelectrochemical activity, and H2O2 works as a hole scavenger to react with light‐induced electron holes on the valence band of BiVO4. Upon illumination and at applied bias potential of +0.2 V, the photocurrent density is linearly correlated to the concentration of H2O2. The linear determination range of H2O2 is 9.54–764.76 μM with a corresponding correlation coefficient of 0.9997, a detection limit of 1.59 μM (S/N=3), and sensitivity of 182.6 μA mM−1 cm−2. The optimum bias potential, most suitable film thickness, anti‐interference performance, and impedance are also explored. The sensor shows good response towards H2O2 and displays a promising prospect for non‐enzyme PEC H2O2 sensor.