In this paper, CeVO4 materials were developed as highly efficient biomimetic catalysts for the first time to detect H2O2. These CeVO4 materials were prepared by a facile hydrothermal method with the assistance of EDTA, exhibiting different morphologies, surface properties, and distinct peroxidase mimetic activities. Among them, CeVO4-2 nanorods (NRs) were proved to display the best intrinsic peroxidase-like property compared to other CeVO4 samples due to their more negative potential and larger BET specific surface area, which 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 excellent peroxidase mimetic catalytic activity of CeVO4-2 NRs, a simple, convenient and visual H2O2 detection system was successfully established. The detection limit of H2O2 could reach as low as 0.07 μM. Moreover, the CeVO4-2 NR-based assay system presented an excellent selectivity, practicability, long-term stability, and reusability. The peroxidase-like catalytic mechanism of CeVO4-2 NRs was proposed on the basis of active species trapping experiments. This work provides a novel, convenient, rapid, and ultrasensitive system for the colorimetric detection of H2O2, which has a bright prospect in H2O2 detection and biomedical analysis.