Ab initio molecular dynamics (MD) is used to investigate NO reaction processes on the (001) surface of CaO. A novel path is proposed for the first steps of nitrogen oxides reactivity catalyzed by the CaO surface. The mechanism consists of the formation of anionic dimers, adsorbing on the surface cations, at the expense of oxidized NO species adsorbed on surface anions. The complete charge-transfer process takes place in two steps, producing, first monovalent anionic dimers (NO)(2)(-) and, later on, divalent anionic dimers (NO)(2)(-). These redox processes cause spin quenching and are observed in the short time scale of the ab initio MD simulation at 300 K. The results presented provide a rationalization of a recent electron spin resonance (ESR) investigation indicating that the spectroscopy is silent to most of the nitrogen oxide species adsorbed on CaO powders, despite deposition of paramagnetic NO molecules at room temperature.