The application and research of high entropy alloy electrodes in urea oxidation reactions (UOR) are significant. In this study, FeCoNiCrMn, FeCoNiCrMnO, and FeCoNiCrMnC high entropy alloy thin films were prepared by magnetron sputtering by controlling the sputtering power, varying the sputtering atmosphere, and using double target co-sputtering, respectively. The microstructure and surface morphology of the electrode were observed and analyzed by X-ray diffraction, scanning electron microscope, transmission electron microscope, and atomic force microscope. In addition, the chemical state of the elements on the electrode surface was analyzed by X-ray photoelectron spectroscopy (XPS) to clarify the mechanism related to the excellent UOR performance of the electrode. The study found that a small amount of carbon doping can greatly improve the UOR performance of this type of electrode. The amorphous FeCoNiCrMnC electrode has more potential UOR active sites than the face-centered cubic FeCoNiCrMn electrode. After cyclic voltammetry (CV), the potential active sites of the electrode are activated, and the active substances of these electrodes are increased, furthermore, the UOR performance of these electrodes has improved. Since it has 200 cycles of CV, the 10 mA cm−2 potential of FeCoNiCrMnC electrode for UOR is only 1.337 V. After 100 days of natural aging, the catalytic ability of the electrode not only did not decrease but slightly improved, with a potential of 1.321 V at 10 mA cm−2, reflecting the good stability of the catalytic electrode.