A new class of high temperature lubricant of inorganic alkali metal polyphosphate was developed for hot metal forming, which involved a fundamental knowledge of melt lubrication. At elevated temperature a 55% reduction in friction and a 50% decrease in wear were achieved by the presence of the molten polyphosphate lubrication, as well as the excellent anti-oxidation capability at the rubbing steel/steel interface, which closely correlated with the tribo-induced hierarchical structure at the rubbing interface. This inorganic polyphosphate lubricant can be called a smart polymeric material, which will be an eco-friendly alternative for high temperature applications.