Rational design and construction of the finest electrocatalytic materials are important for improving the performance of electrochemical sensors. Spinel bioxides based on cobalt manganate (CoMn 2 O 4 ) are of particular importance for electrochemical sensors due to their excellent catalytic performance. In this study, three-dimensional CoMn 2 O 4 with the petal-free, flowerlike structure is synthesized by facile hydrothermal and calcination methods for the electrochemical sensing of roxarsone (RXS). The effect of calcination temperature on the characteristics of CoMn 2 O 4 was thoroughly studied by in-depth electron microscopic, spectroscopic, and analytical methods. Compared to previous reports, CoMn 2 O 4 -modified screen-printed carbon electrodes display superior performance for the RXS detection, including a wide linear range (0.01−0.84 μM; 0.84−1130 μM), a low limit of detection (0.002 μM), and a high sensitivity (33.13 μA μM −1 cm −2 ). The remarkable electrocatalytic performance can be attributed to its excellent physical properties, such as good conductivity, hybrid architectures, high specific surface area, and rapid electron transportation. More significantly, the proposed electrochemical sensor presents excellent selectivity, good stability, and high reproducibility. Besides, the detection of RXS in river water samples using the CoMn 2 O 4 -based electrochemical sensor shows satisfactory recovery values in the range of 98.00−99.80%. This work opens a new strategy to design an electrocatalyst with the hybrid architecture for high-performance electrochemical sensing.