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[Display omitted] • AgCo-g-CN possessed enhanced catalytic decomposition of N 2 O under O 2 compared with Co 3 O 4. • Metallic Ag and higher content of Co2+ were found on AgCo-g-CN by adding g-CN. • Higher contents of Co2+ could play a beneficial role in the enhancement of N 2 O catalytic decomposition. • Metallic Ag improved the O 2 desorption capacity of AgCo-g-CN. Nitrous oxide (N 2 O) has gained increasing attention as an important greenhouse gas and stratospheric-ozone-depleting substance. Catalytic decomposition is considered an effective method for N 2 O abatement. Herein, AgCo-g-CN catalyst prepared by impregnation synthetic procedure was tested for N 2 O catalytic decomposition in the presence of O 2. The catalytic results indicated that full N 2 O conversion was obtained at 400 °C. The enhancement of catalytic activity was mainly derived from the addition of g-CN compared with bare Co 3 O 4 and AgCo. Metallic Ag and higher content of Co2+ were found over the AgCo-g-CN catalyst. By XPS and kinetic analysis, the catalytic performance was correlated with the content of Co2+, the facilitation of Co2+ contents could play a beneficial role in the enhancement of the AgCo-g-CN catalysts. Besides, HRTEM, XPS, and TPx revealed that metallic Ag improved the O 2 desorption capacity of AgCo-g-CN, which is important during the N 2 O catalytic decomposition. By lowering the valence of Co and Ag species, g-CN enhanced the catalytic performance of N 2 O. This study might provide a reference for designing N 2 O decomposition catalysts and potential applications for g-CN in heterogeneous catalysis. [ABSTRACT FROM AUTHOR]