A series of Cs promoted NiO catalysts have been prepared and tested for direct decomposition of N2O. These catalysts are characterized by BET surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of N2O (TPD-N2O) and X-ray photo electron spectroscopy (XPS). The Cs promoted NiO catalysts exhibit higher activity for the decomposition of N2O compared to bulk NiO. The catalyst with Cs/Ni ratio of 0.1 showed highest activity. The enhancement in catalytic activity of the Cs promoted catalysts is attributed to the change in the electronic properties of NiO. The characterization techniques suggest weakening of Ni-O bond thereby the desorption of oxygen becomes more facile during the reaction. The Cs promoted NiO catalyst is effective at low reaction temperature and also in the presence of oxygen and steam in the feed stream.