The contact angles of the aqueous solution of ethanol and that of n-propanol on copper, aluminum, and stainless steel surfaces are reported. The contact angles were measured under atmospheric conditions, and then under vapor-liquid equilibrium conditions at 1 atm and different temperatures. The results showed the variations of the contact angles with the concentrations of aqueous solutions on different metal material surfaces with different roughness. Some unstable behavior of the wetting ability around the azeotropic point of a binary solution is reported. Influences of concentration, kind of materials, and the surface roughness on the wetting ability are discussed. The model for predicting the contact angle of alcohol aqueous solutions on metal surfaces under atmospheric and vapor-liquid two-phase equilibrium conditions at 1 atm is derived from the Young equation.