Understanding the properties of polymer–metal interfacial friction is critical for accurate prototype design and process control in polymer-based advanced manufacturing. The transient polymer–metal interfacial friction characteristics are investigated using united-atom molecular dynamics in this study, which is under the boundary conditions of single sliding friction (SSF) and reciprocating sliding friction (RSF). It reflects the polymer–metal interaction under the conditions of initial compaction and ultrasonic vibration, so that the heat generation mechanism of ultrasonic plasticization microinjection molding (UPMIM) is explored. The contact mechanics, polymer segment rearrangement, and frictional energy transfer features of polymer–metal interface friction are investigated. The results reveal that, in both SSF and RSF modes, the sliding rate has a considerable impact on the dynamic response of the interfacial friction force, where the amplitude has a response time of about 0.6 ns to the friction. The high frequency movement of the polymer segment caused by dynamic interfacial friction may result in the formation of a new coupled interface. Frictional energy transfer is mainly characterized by dihedral and kinetic energy transitions in polymer chains. Our findings also show that the ultrasonic amplitude has a greater impact on polymer–metal interfacial friction heating than the frequency, as much as it does under ultrasonic plasticizing circumstances on the homogeneous polymer–polymer interface. Even if there are differences in thermophysical properties at the heterointerface, transient heating will still cause heat accumulation at the interface with a temperature difference of around 35 K.