The dependence between the conformation of polystyrene (PS) and its molecular weight (Mw) in the vicinity of a metal interface was investigated by sum frequency generation (SFG) spectroscopy. Tilt angles θ ≥ 50° (the angle between the C2 axis of the pendant phenyl ring and the surface normal) were observed for all samples because of the interaction between the aromatic rings and the metal surface. Furthermore, it was found that θ decreases with increasing Mw for PS samples ranging from 20 × 103 g/mol to 400 × 103 g/mol. The intensity of the backbone SFG signal was higher for high Mw PS, compared to low Mw PS, indicating a greater number of backbone interactions with the silver substrate surface for the high Mw sample. These structural differences are driven by different entropic and enthalpic contributions to the free energy of adsorption for different polymer molecular weights. Differences in the polymer free volume and in the relative amount of chain ends with higher mobility may also influence the chain conformation. These results suggest that important interfacial properties of polymeric thin films, such as adhesion and wettability, could be tailored by modifying the polymer Mw to achieve the desired interfacial conformation.