A successful application of a hot dip coating process that coats aluminum (Al) on aluminum nitride (AlN) ceramics, revealed that Al had a perfect wettability to the ceramics under specific circumstances, which was different from previous reports. In order to elucidate the mechanism that controlled the supernormal wetting phenomenon during the dip coating, a first-principle calculation of an Al(111)/AlN(0001) interface, based on the density functional theory (DFT), was employed. The wettability of the Al melt on the AlN(0001) surface, as well as the effect that the surface reconstruction of AlN and the oxygen adsorption had on Al for the adhesion and the wettability of the Al/AlN system, were studied. The results revealed that a LCM (laterally contracted monolayer) reconstruction could improve the adhesion and wettability of the system. Oxygen adsorption on the free surface of Al decreased the contact angle, because the adsorption reduced of the surface tension of Al. A prefect wetting was obtained only after some of the oxygen atoms adsorbed on the free surface of Al. The supernormal wetting phenomenon came from the surface reconstruction of the AlN and the adsorption of oxygen atoms on the Al melt surface.