Recent studies on two-dimensional layered materials under external electric fields have gained significant attention, as such fields offer a powerful, non-invasive approach to actively modulate surface interactions at the molecular level, enabling real-time and reversible tuning of material properties. In this Letter, using fully atomistic molecular dynamics simulations based on machine-learning potentials to predict the dependence of chemifriction on external electric fields in defected layered contacts. By controlling the rate of polar bond formation and rupture friction can be either increased or decreased depending on the field strength and direction. To extend these atomistic insights to the experimentally relevant low-velocity regime, we develop a physically motivated stochastic model that bridges atomic-scale mechanisms with macroscopic friction behavior. Although demonstrated for h-BN junctions, the proposed mechanism of electro-tunable chemifriction is expected to be general and applicable to a broad range of layered materials with polar interlayer bonding.