Total internal reflection infrared (IR) absorption and visible-IR sum-frequency spectroscopies were used to study the role of acrylic acid in the evolution of surface structure in a poly(butyl acrylate)-based pressure-sensitive adhesive during the drying process. By monitoring these spectral responses and calculating the heterospectral correlation coefficients, we established that acrylic acid alters the nature of the molecular interactions at the surface. In the absence of acrylic acid, butyl acrylate orientation is driven by the packing of the polymer as the water evaporates. When acrylic acid is present, a rapid ordering of the copolymer takes place as a result of favorable hydrogen-bonding interactions with the surface.