An ab initio study of the A′1 ground potential energy surface (PES) of the O(1D)+N2O(X 1∑+) system has been performed at the CASPT2//CASSCF (complete active space second-order perturbation theory//complete active space self-consistent field) level with Pople basis sets. The two reactions leading to 2 NO(X 2∏) [reaction (1)] and N2(X 1∑g+)+O2(a 1Δg) [reaction (2)] products have been investigated. In both reactions a trans-approach of the attacking oxygen to the N2O moiety is found to be preferred, more markedly in reaction (1). For this reaction also a cis-path is feasible and is possibly connected with the trans-path by a transition state placed below reactants. A thorough characterization of the entrance zone has been performed to allow for subsequent kinetics calculations. Fixed angle and minimum energy paths have been constructed and transition state geometries have been refined at the CASPT2 level, thus obtaining approximate structures and frequencies for the latter. From these calculations it can be inferred that both reactions proceed without an energy barrier. Rate constant calculations in the 100–1000 K temperature range based on CASPT2 structures and using the transition state theory yield values in good agreement with experiment for the two reactions, especially when a proper scaling of the energy barriers is performed. Also, for comparative purposes quasiclassical trajectory calculations were performed on reaction (1) in the same temperature range, using a previous pseudotriatomic analytical potential energy surface, obtaining good agreement with experiment.