The rapid electrification of mechanical systems has intensified concerns about the effect of electrical potential on the tribological performance of polymer components used in electric drivetrains. Reciprocating ball-on-disk tribological tests were performed using a carbon-fiber-reinforced polyetheretherketone (PEEK CF30) disc sliding against an AISI 52100 steel ball under dry conditions while different DC voltages were applied across the contact. The results indicate that electrical potential affects the tribological behavior of the PEEK CF30/steel pair. In zero and low-to-moderate potentials (up to 10 V) the wear remains in the same range (10−7 mm3/Nm), while a potential of 20 V increases the wear by one order of magnitude to 6.76× 10−6 mm3/Nm. The friction also increased by 25%, achieving a value of 0.30 compared to the 0-V condition. However, at a high potential of 30 V, a softening effect becomes dominant, which in turn reduced the wear by three times to 2.08 × 10−6 mm3/Nm, accompanied by a friction decrease of 40%, reaching 0.19 relative to the 20-V condition. These findings demonstrate that electrical potential influences the tribological performance of polymeric composites reinforced with carbon fiber. The failure mechanisms in electrified tribological contacts are discussed for situations where the electric current acts as a tribo-chemical activation mechanism, the effects of which depend on the applied potential and the polymer composite's structure, promoting electrochemical reactions, Joule heating, accelerated wear, material transfer, and interfacial degradation.