The propylene epoxidation reaction in a rich variety of other industrially important catalytic processes was used for synthesis of many value-added products. As an attractive and environmentally friendly process for direct epoxidation of propylene by Cu-based catalysts, the active oxidation states of Cu (Cu0, Cu+, or Cu0/Cu+) in the epoxidation reaction were widely studied. Herein, “29” CuxO/Cu(111) was chosen to act as a precursor to bulk oxidation, as it can be observed in special oxide phases of Cu (Cux+). In our work, the crucial competitive reactions of dehydrogenation versus the epoxidation using the lattice oxygen (Olatt*) and adsorbed molecular oxygen as the oxidants were investigated on “29” CuxO/Cu(111) surface by virtue of the periodic density functional theory computational method. Because of the higher energy barriers of the key steps for the lattice oxygen (Olatt*) as the oxidant, there are two active species in the whole reaction processes of propylene oxidation with O2 as oxidant: the molecular O2* species and the atomic O* species. It was found that the molecular oxygen is difficult to dissociate on the surface directly, while the atomic O* species can be produced via the C3H6* + Olatt* + OO* = C3H5* + Olatt* + OOH* = C3H5Olatt* + O* + OH* mechanism or by the mechanism of C3H6* + OO* = dioxametallacycle = oxametallacycle + O*. It was found that the O* mechanism is preferred for the PO formation as compared to that of O2* on pure “29” CuxO/Cu(111) surface. Promising results in terms of selectivity were achieved for PO formation, which can reach 49% with the apparent activation energy of only 0.62 eV by microkinetic simulation. Therefore, “29” CuxO/Cu(111) surface involving the Cux+ active phase is expected to show an efficient PO selectivity, which is much higher that of Cu+ of Cu2O(111) and similar to that of metallic Cu0. It is hoped that the present study could provide a theoretical guide for the further development of catalysts for propylene epoxidation.