The adsorption and surface reactions of NO on a VO/V(110) surface have been investigated using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure, and temperature programmed desorption (TPD) technique. NO is molecularly adsorbed on VO/V(110) at 80 K. As the surface coverage of NO increases, the NO dimer is formed on the surface at 80 K. Both NO and (NO)2 are adsorbed on the surface with the N-O bond perpendicular to the surface. (NO)2 decomposes at ~100 K and the reaction product is desorbed as N2O. Decomposition of NO takes place when the surface temperature is higher than 273 K.