The paper deals with the temperature dependence of the contact angle of wetting of a steel substrate with a liquid tin. The experiment shows that the wetting angle is decreased as the temperature rose, and the wettability of this system is improved. However, with the further increase in temperature, the contact angle is increased again that is an abnormal phenomenon. To explain this phenomenon and the process of contact-angle formation in general, we propose the quantum mechanical model based on the Wentzel–Kramers–Brillouin (WKB) conception. In this case, interaction of the melt ions with the substrate atoms is considered indirectly through the formation of a potential barrier with the linear dimensions determined by both the ratio of masses of the atoms of interacting metals and the temperature. From the WKB standpoint, at low temperatures, when the kinetic energy of a generalized particle with the reduced mass is less than the potential barrier, the wave function decays rapidly and, accordingly, the contact angle does not actually change. Quantitative and qualitative changes appear, when the kinetic energy of particles with the reduced mass exceeds the positive barrier values because of increase in temperature. Following the WKB conception, passage or reflection of a particle with the reduced mass over the barrier is determined by the integer or half-integer ratio of the de Broglie wavelength and linear dimensions of the potential barrier. Therefore, qualitative changes in the system, i.e., the wetting threshold and abnormal increase in the contact angle, are described by the processes associated with passage or reflection of a particle with the reduced mass over the barrier. Experimental and theoretical curves of dependences of both the contact angle and the work of adhesion versus temperature show similar dynamics.