The triboelectrification electrostatic potential of MC nylon 6 and its influence factors have not been investigated to date. Here, we report on our study of the interaction of tribological behaviors and triboelectrification electrostatic potential for the prevention or application of triboelectrification. The equipment we used to polymerize insulation materials and for instantaneously monitoring the dynamic variations of triboelectrification electrostatic potential, friction coefficient, and temperature at the tribointerface was self-designed. The dynamic variations in the triboelectrification electrostatic potential of the polymer insulation materials under dry sliding were investigated using this equipment. An obvious influence on magnitude and change tendency of the triboelectrification electrostatic potential of MC nylon 6 could be produced only when the combined action of load (P) and speed (V) made PV values reach a certain degree. After MC nylon 6 rubbing against the bearing steel, the triboelectrification electrostatic potential of MC nylon 6 was not constant, and it could even abruptly drop from hundreds of volts to 0, especially under severe sliding conditions. A positive charge existed on the tribo-surface of MC nylon 6 and a negative charge existed on the tribo-surface of the counterpart steel. During the severe wear process, the experimental conditions, wear rate, the formation of transfer film, and the fraction of film on the counterpart as well as frictional heat were the most significant interaction effects on the abrupt change in the triboelectrification electrostatic potential among all factors studied. The interaction of tribological behaviors and triboelectrification electrostatic potential was clearly not a simple physical mechanism, which might be influenced by the external conditions and internal integration.