Epoxidation of propylene into propylene oxide (PO) in the gas phase is a highly challenging reaction. Cu-based catalysts have been active for this reaction, but the state of Cu as an active species is still debatable. In this paper, we report the propylene epoxidation activity of solution combustion synthesized Cu/CeO2 catalysts with the CO + O2 mixture at low temperatures (50-100 °C) peaking at80 °C. The highest PO yield was obtained with 20-25 Cu loading in CeO2. In contrast, the reaction over the catalyst containing nonreducible support such as Cu/SiO2 occurred above 170 °C. Detailed structural characterization indicated two types of Cu species such as Cu2+ partly (∼3%) dissolved in CeO2 forming a CuxCe1-xO2-δ phase and the remaining amount formed highly dispersed CuO as a separate phase. Thus, the highest activity relates to the optimum presence of CuO along with Ce1-xCuxO2-δ. The reducibility of the Cu species in two phases was significantly shifted toward lower temperatures, indicating strong electronic interaction between the two phases. The substituted Cu2+ was reduced first, and then, the bulk CuO reduction was initiated. In situ spectroscopic studies showed Cu+ formation from Cu2+ over Cu/CeO2 catalysts even at room temperature unlike in CeO2 or CuO + CeO2 physical mixtures, indicating strong electronic interaction between Ce1-xCuxO2-δ and CuO phases on CO adsorption in the Cu/CeO2 catalyst. It is proposed that substituted Cu2+ along with Ce4+ is reduced easily, and then, Ce3+ promotes the reduction of the interfacial CuO phase that might donate active oxygen species for epoxidation reaction.