In this paper, FeVO₄ materials were prepared via a facile hydrothermal method under different pHs and developed as highly efficient biomimetic catalysts for the first time. Different FeVO₄ materials with different crystal structures, morphologies and surface properties showed distinct peroxidase-like activities. Experimental results showed that the products obtained at pH = 4 (FeVO₄-4) possessed a belt-like nanostructure with a large BET specific surface area and exhibited the best intrinsic peroxidase-like activity compared to other FeVO₄ materials. FeVO₄-4 nanobelts (NBs) could efficiently catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H₂O₂ to generate a blue oxide. Based on the highly efficient catalytic activity of FeVO₄-4 NBs, a novel system for optical determination of H₂O₂ was successfully established, and the detection limit of H₂O₂ could reach 0.2 μM. FeVO₄-4 NBs also exhibited excellent selectivity, reproducibility, long-term stability, and easy recovery property. Furthermore, a peroxidase mimetic mechanism of FeVO₄-4 NBs was proposed based on the active species trapping experiments. This work developed a novel, accessible and highly sensitive system for visual detection of H₂O₂, making FeVO₄-4 NBs a potential biomimetic catalysts in H₂O₂ detection and biomedical analysis.