β-Mn type Co–Zn–Mn is a chiral magnet hosting Bloch type magnetic skyrmions and has been extensively studied because the magnetic skyrmions are observed above room temperature depending on the composition of Co, Zn, and Mn. So far, epitaxially grown film of Co–Zn–Mn on single crystal substrates has not been not realized whereas the epitaxial film is important from the fundamental and practical point of view. In this study, Co–Zn/Mn multilayered film was sputter-deposited on MgO(001) single crystal substrate and then annealed in vacuum for the crystallization of Co–Zn–Mn alloy. β-Mn type Co–Zn–Mn epitaxial film with (001) orientation was successfully fabricated although the film consisted of twinned crystal grains. We also showed that the annealing of 300–350 °C was effective to drive the crystallization, and that the possibility to enhance the crystallinity by optimizing the fabrication conditions.