High-purity hydrogen is extensively employed in chemical vapor deposition, and the existence of methane impurity significantly impacts the device performance. Therefore, it is necessary to purify hydrogen to remove methane. The ZrMnFe getter commonly used in the industry reacts with methane at a temperature as high as 700 °C, and the removal depth is not sufficient. To overcome these limitations, Co partially substitutes Fe in the ZrMnFe alloy. The alloy was prepared by suspension induction melting method, and was characterized by means of XRD, ICP, SEM and XPS. The concentration of methane at the outlet was detected by gas chromatography to characterize the hydrogen purification performance of the alloy. The removal effect of the alloy on methane in hydrogen increases first and then decreases with the increase in substitution amount, and increases with the increase in temperature. Specifically, the ZrMnFe0.7Co0.3alloy reduces methane levels in hydrogen from 10 ppm to 0.215 ppm at 500 °C. ZrMnFe0.7Co0.3alloy can remove 50 ppm of methane in helium to less than 0.01 ppm at 450 °C, demonstrating its excellent methane reactivity. Moreover, Co substitution reduces the formation energy barrier of ZrC, and Co in the electron-rich state demonstrates superior catalytic activity for methane decomposition.