Over the past twenty years, thin film lubrication (TFL) theory has been used to characterize the molecular behaviors in lubrication films thinner than 100 nm, effectively bridging the gap between elastohydrodynamic lubrication and boundary lubrication. Unfortunately, to date, the TFL molecular model proposed in 1996 has not been directly proven by experimental detection. Herein, a method based on surface-enhanced Raman spectroscopy was developed to show both the packing and orienting of liquid molecules in the TFL regime. By trapping liquid crystal molecules between a structured silver surface and a glass surface, molecular ordering states dominated by shear effect and surface effect were successfully distinguished. A nanosandwich structure consisting of an adsorbed layer, an ordered-molecule layer, and a fluid layer was demonstrated. Molecule imaging in TFL was achieved. Our results illustrate the molecular behaviors and lubrication mechanism in nanoconfined films and facilitate the lubrication design of nanoelectromechanical and microelectromechanical systems.