This work was aimed to design efficient catalysts for N2O decomposition at low temperatures. Cobalt oxide (Co3O4) was prepared by hydrothermal, precipitation and combustion methods and tested for N2O decomposition. It was found that the catalysts prepared by solution combustion synthesis were most active for this reaction. Subsequently, a series of ceria (CeO2) supported Co3O4 catalysts (xCeCo) were prepared by solution combustion method and used them for N2O decomposition. All the catalysts were characterized by analytical methods like XRD, TEM, BET, XPS, UV-Vis, Raman and H 2-TPR. It was found that 10 and 20 wt.% loading of CeO2 on Co3O4 promoted the activity of Co3O4 towards N2O decomposition, whereas, higher loading of CeO2 reduced the activity. Typical results indicated that addition of CeO2 increases the surface area of Co3O4, and improves the reduction of Co3+ to Co2+ by facilitating the desorption of adsorbed oxygen species, which is the rate-determining step for the N2O decomposition over Co3O4 spinel catalysts. Optimal CeO2 loading can increase both dispersion and surface area of Co3O4 catalysts and weaken the Co–O bond strength to promote N2O decomposition. [Figure not available: see fulltext.] © 2016, Indian Academy of Sciences.