Exploring highly efficient electrocatalysts is crucial for aprotic Li-O2 batteries. Pd/NiO nanomembranes with hierarchical pores are fabricated and employed as cathode catalysts in Li-O2 batteries. By means of standard photolithography, ordered macropores were prepared in the nanomembranes. Moreover, we developed a facile template-free method to create nanopores with sizes ranging from 50 to 200nm in the composite. The diverse pores of micro- and nanometer sizes and the resulting loose structure supply fast channels for the transportation of reactants, thus efficiently promoting the performance of Li-O2 batteries by lowering the overvoltages and enhancing the rate capability and stability.