The performance and durability of mechanical/tribological systems in electric vehicles (EVs) are significantly influenced by the use of lubricants capable of withstanding electrical stress. The study presents a high-performance nitrogen- and phosphorus-based ionic liquid (N/P IL) additive, specifically designed to adapt to the electrified steel tribopair (AISI 52100), forming a durable and antiwear tribofilm. The study aims to comprehend the mechanisms underlying oil physicochemical properties and tribofilm formation using advanced analytical techniques. The SRV-IV tribometer was used for triboelectrification tests under varying sliding conditions at 0–10 A DC currents. The 1.5-N/P-IL oil forms a durable tribofilm (up to 414.5 nm thickness) through positive triboelectrochemical reactions. As a result, the 1.5-N/P-IL oil achieved a decrease of 33% in the friction coefficient and an 82% decrease in the wear rate of the tribopair under triboelectrification events compared to commercial ATF-EV oil. Furthermore, the 1.5-N/P-IL oil maintains effective lubrication performance over a wide temperature range up to 175°C. Notably, the morphological analysis offers a smoother surface without signs of wear damage. Eventually, this research provides valuable insights into the N/P IL additive for programmable friction control and durable/antiwear tribofilm formation under triboelectrification effects.