Unraveling the microscopic mechanisms governing the coupling between interfacial friction and sliding ferroelectricity is pivotal for advancing ultra-low-friction tribology and high-speed nonvolatile memory technologies. Here, we introduce ΔW, defined as the variation in orbital weight within a physically motivated energy window (~0.1 eV) for the uppermost occupied states bounded by the Debye energy scale, as an effective electronic descriptor that bridges interfacial friction and ferroelectric polarization across two-dimensional van der Waals multilayers, atomically thin films, and three-dimensional bulk ferroelectrics. ΔW is intrinsically correlated with the spin-polarized electronic structure near the Fermi level, and is intimately linked to both phonon-mediated energy dissipation and ferroelectric soft-mode dynamics. We demonstrate that the minimum-energy friction pathway coincides exactly with the ferroelectric switching trajectory. Along this pathway, sliding friction (f), ferroelectric polarization (P), and ΔW evolve synchronously, giving rise to robust linear scaling relationships: f ∝ ΔW and P ∝ ΔW. This scaling behavior persists regardless of orbital character, external pressure, finite temperature, or magnetic ordering effects. Our findings establish ΔW as a tunable quantum target for the concurrent optimization of ultralow friction and superior ferroelectric performance, paving the way for the rational design of energy-efficient interfacial systems and next-generation nanodevices.