Controlling the surface molecular structure of spin cast polymer films is important for the rational design of surface properties. However, the relationship between spin casting parameters and film surface molecular structure is poorly understood. We report that the surface molecular structure of spin cast homopolymers which contain phenyl groups is influenced by the solvent aromaticity, investigated by a nonlinear optical spectroscopy, sum frequency generation (SFG) vibrational spectroscopy. When phenyl groups were located in a linear polymer backbone, spin casting with aromatic solvents enhanced the phenyl SFG signal relative to when a non-aromatic solvent was used which suggests that the aromatic solvent induced the surface phenyl groups to be more ordered and/or to lie more perpendicular to the film surface. In addition, when alkyl structures were believed to be present at the solvent/air interface, alkyl structures were observed at the film/air interface which suggests that molecular structure at the solvent/air interface was carried to the film surface. The effects of solvent aromaticity on phenyl ordering at spin cast film surfaces can be explained by different molecular structures of polymer chains at solvent/air interfaces, preferential solvation of functional groups during evaporation, and re-orientation of bulky side groups at the polymer film/air interface.