The adsorption and dissociation of borazine were investigated on Rh(111) single crystal surface by Auger electron spectroscopy (AES), high resolution electron energy loss spectroscopy (HREELS) and temperature programmed desorption (TPD) methods. Borazine is one of the most frequently applied precursor molecules in the preparation process of boron nitride overlayer on metal single crystal surfaces. On Rh(111) surface it adsorbs molecularly at 140 K. We did not find any preferred orientation, although there is evidence of “flat” and perpendicular molecular geometry, too. Dehydrogenation starts even below 200 K and finishes until ∼7-800 K. No other boron or nitrogen containing products were observed in TPD beyond molecular borazine. Through the hydrogen loss of molecules hexagonal boron nitride layer forms in the 600-1100 K temperature range as it was indicated by AES and the characteristic optical phonon HREEL losses of h-BN overlayer. The adsorption behaviour of the boron nitride covered surface was also studied through the adsorption of methanol at 140 K. HREELS and TPD measurements showed that methanol adsorbed molecularly and a fraction of it dissociated to form surface methoxy and gas phase hydrogen on the h-BN/Rh(111) surface.