Copper-ceria (Cu-Ce) catalysts with unique catalytic properties have high prospects as alternatives for noble metals in low-temperature catalytic oxidations. However, the quantitative description of the active sites in the redox processes still remains a challenge. Herein, a series of Cu-Ce catalysts were prepared by regulating the synthesis method, AR_Cu/Ce (atomic ratios of Cu to Ce), and pH of precipitation, so as to investigate CO and VOCs oxidations. Cu⁺-O_V-Ce³⁺ configuration, as an asymmetric oxygen vacancy (ASO_V), was formed in the copper-ceria interface. Its concentration was accurately regulated under varying pH, and was quantificationally identified by ex-situ techniques in static conditions. The maximum ASO_V concentration was recorded for the CuCe3–11 catalyst, accounting for the best catalytic activity and stability. Moreover, the dynamic exchange behaviors (Cu⁺-O_V-Ce³⁺↔ Cu²⁺-O^2-_(ad)-Ce⁴⁺) of the ASO_V were quantificationally studied by in-situ techniques under the same reaction conditions. In the oxygen-containing reaction, 13% ASO_V was first converted to Cu²⁺-O^2-_(ad)-Ce⁴⁺ species, and then wholly recovered in the presence of CO. In the CO oxidation processes, the dynamic exchange of ASO_V maintained equilibrium under T₅₀ and T₁₀₀. This work offers future prospects for the quantification tracking of the active sites in catalysts, while also providing a universal strategy for the rational fabrication of high-performance environmental catalysts.