Selective oxidation of olefins to desired products such as epoxides is highly demanded in chemical industry. It remains challenging to achieve high selectivity for production of epoxides over heterogeneous catalysts through using molecular oxygen as the oxidant. Nanoporous reverse catalysts (MoO3@np-Au) consisting of pure nanoporous gold (np-Au) and MoO3 nanoparticles anchored on Au ligaments were synthesized for selective oxidation of cyclohexene with molecular oxygen. By controlling the loading of molybdenum and thermal treatment condition, MoO3 nanoparticles with size of 5 nm were uniformly anchored on the surface of gold ligaments (30-50 nm) of pure nanoporous gold (np-Au). These synthesized MoO3@np-Au catalysts exhibited high selectivity of 58%-73% for production of cyclohexene oxide at conversion of 4%-11% of cyclohexene by using molecular oxygen as the oxidant. Compared to MoO3@np-Au, the selectivity for the production of cyclohexene oxide on pure np-Au catalyst is only 6% under the same catalytic condition as that on MoO3@np-Au. The observed high selectivity for production of cyclohexene oxide on MoO3@up-Au can be rationalized with a bi-functional mechanism of a reverse metal/oxide catalyst. The in-situ formed surface molybdenum oxo-peroxo species are suggested to be responsible for selective oxidation of cyclohexene to cyclohexene oxide, while the MoO3/Au interface activates molecular oxygen to regenerate the molybdenum oxo-peroxo active centers. (C) 2016 Published by Elsevier B.V.