To develop a novel shearing resin material, it is necessary to understand the mechanism of friction-induced chemistry during the friction process. For this purpose, the chemical reaction of the polytetrafluoroethylene (PTFE) resin on an aluminum surface during friction was first focused on and investigated by a quantum chemical molecular dynamics method. From our simulation, an aluminum atom on a native oxide of aluminum surface led to a tribochemical reaction, which included defluorination of PTFE and aluminum fluoride formation. It was inferred that the aluminum surface acted as a catalytic Lewis acid in which the fluorine atom was removed from the PTFE polymer chain. The tribological performance of the investigated system was reduced by the forming of aluminum fluoride since a self-lubrication by PTFE was inhibited by an interfacial electrostatic repulsion. On the basis of our study, it was suggested that the key to increase tribological performance was a chemical reaction between reactive defluorinated PTFE and environmental water vapor to form a novel functional group on the PTFE chain.