The selection of elements, tune of compounds types and modification of structure are important ways to improve OER activity of high-entropy alloys. The reconstruction behavior of film electrodes during OER process revealed that Mo element has a strong promoting effect on the reconstruction of FeCoNi-based films. It is shown by first-principles that electron-deficient region could be formed near Mo, and electron-rich region could be formed near surrounding elements of Mo. Charge transfer may be the reason that Mo promotes reconstruction of high-entropy alloys. Compared with FeCoNiCr film electrode, FeCoNiCrMo film electrode, the 2p3/2 binding energy peaks of Fe/Co/Ni in which are shifted forward, has more oxygen-containing species and oxygen vacancies. The study also revealed the existence of lattice oxygen mechanism during OER process. The deposition thickness of alloy film has a linear relationship with sputtering time and deposition rate of FeCoNiCrMo. There is an optimal deposition thickness of FeCoNiCrMo film electrode for OER. FeCoNiCrMo film electrodes have the most excellent OER performance: the overpotential is 268 mV, and the Tafel slope is 57.6 mVdec−1.