||We have investigated the adsorption and thermal reaction processes of NO with silicene spontaneously formed on the ZrB2/Si(111) substrate using synchrotron radiation x-ray photoelectron spectroscopy (XPS) and density-functional theory calculations. NO is dissociatively adsorbed on the silicene surface at 300 K. An atomic nitrogen is bonded to three Si atoms most probably by a substitutional adsorption with a Si atom of silicene (N≡Si3). An atomic oxygen is inserted between two Si atoms of the silicene (Si—O—Si). With increasing NO exposure, the two-dimensional honeycomb silicene structure gets destroyed, judging from the decay of typical Si 2p spectra for silicene. After a large amount of NO exposure, the oxidation state of Si becomes Si4+ predominantly, and the intensity of the XPS peaks of the ZrB2 substrate decreases, indicating that complicated silicon oxinitride species have developed three-dimensionally. By heating above 900 K, the oxide species start to desorb from the surface, but nitrogen-bonded species still exist. After flashing at 1053 K, no oxygen species is observed on the surface; SiN species are temporally formed as a metastable species and BN species also start to develop. In addition, the silicene structure is restored on the ZrB2/Si(111) substrate. After prolonged heating at 1053 K, most of nitrogen atoms are bonded to B atoms to form a BN layer at the topmost surface. Thus, BN-covered silicene is formed on the ZrB2/Si(111) substrate by the adsorption of NO at 300 K and prolonged heating at 1053 K.