We have studied the UV-laser-induced desorption of NO adsorbed on an epitaxial film of NiO(111) grown on Ni(111). The desorbing molecules were detected state selectively via a resonance enhanced ionization technique [REMPI(1+1)] using the A (2) Sigma(upsilon’=0,1,2)<--X (2) Pi(upsilon"=0,1,2) transition as intermediate state. Our results are compared with our experiments on NO desorption from NiO(100). The similarities and differences of the results due to the different surface structure of the polar NiO(111) and the non polar NiO(100) are discussed. For both surfaces we observe bimodal velocity flux distributions independent of the rovibrational state. Due to a rotational temperature of about 400 K and a vibrational temperature of 1800 K thermal processes can be ruled out. The wavelength dependence of the desorption cross section strongly correlates with the electronic structure of the NiO indicating a surface mediated excitation process. The spin orientation in the NO molecules influences the life time of the excited state depending on the magnetic property of the NiO surface.