Hot rolling with a large reduction is usually performed to produce the fine-grained strips, which leads to a severe wear of work roll and affect substantially the strip quality. As a result, lubricants are usually introduced to reduce these problems, with inorganic polyphosphate glass polymer showing the most promising prospective. This study aims to provide a new insight into the lubrication film at roll/strip interface in hot rolling. A series of lubricated hot rolling tests were performed by a 40wt% sodium metaphosphate aqueous solution under 20–60% reduction, at 950–1150 °C and 0.5 m/s. Thermal behaviors of sodium polyphosphate and the rolled strip samples were analyzed by high temperature laser confocal microscope, Secondary Electron Microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDX), Focused Ion Beam (FIB) and Transmission Electron Microscopy (TEM) etc. The results reveal that the lubrication film thickness at the roll/strip interface varied from 0.6 to 4.3 µm with the rolling load being reduced up to 6.1% and friction coefficient up to 16%. FIB and TEM analysis reveal that the polyphosphate film has an amorphous structure which was penetrated through by the oxide scale. It had been found that the polyphosphate lubrication performance was improved at a higher reduction and temperature, which contributes to the friction and oxidation-reduction.