Vibrationally resonant sum frequency generation (VR-SFG) is used to determine the structure of the phenyl side groups of deuterated polystyrene at the liquid/solid interface for the nonsolvent liquids hexane, methanol, ethanol, glycerol, and water. The structure for the three low-surface-tension (gamma) liquids-hexane, methanol, and ethanol-is similar and only slightly perturbed from that of the air/solid interface. The air interface is ordered with the phenyl rings oriented away from the polymer bulk. The structure for the two high-gamma liquids, water and glycerol, differs significantly from the low-gamma liquids and reflects a near flat orientation of the phenyl ring.