Two-dimensional MnOx nanomembranes prepared by electron beam evaporation are rolled up into three-dimensional hybrid micro/nano-tubes by strain release. The material is characterized with Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), cyclic voltammetry and used as the cathode catalysts for lithium–oxygen (Li–O2) batteries. The Li–O2 battery using such curly MnOx nanomembranes as the cathode delivers a specific discharge capacity of 4610 mAh g C −1 at a current density of 70 mA g C −1 which is higher than that of carbon black. Moreover, the MnOx nanomembrane electrode gains improved stability, being capable of cycling 112 times at a current density of 200 mA g C −1 . The encouraging performance is ascribed to the unique superiorities of nanomembranes and those inner oxygen vacancies, indicating that nanomembranes are promising materials for Li–O2 batteries.