<p>Solid-state sodium metal batteries with inorganic electrolytes have long been heralded as candidates for post-lithium-ion batteries. However, challenges including interfacial instability and air sensitivity continue to impede their path to commercialization. Here, we propose an interfacial healing strategy for solid-state sodium metal batteries by utilizing an electroinitiated accelerated polymerization process facilitated by charged microdroplets to increase the polymerization rate by 21.4 times. We show that the charge-driven electrowetting enables efficient coating layers at interfaces, which impart prolonged air stability and preferentially fill voids and cracks, further constructing stable interfaces with improved compatibility and preventing dendrite-induced crack propagation. A higher critical current density of 6.8 mA cm⁻² is achieved, and assembled cells exhibit prolonged cycling life at 1.0 C over 1000 cycles. In particular, the electroinitiated accelerated polymerization-assisted interfacial healing strategy enables Ah-level pouch cells to undergo stable long-term cycling without any clamping force, demonstrating the capabilities of solid-state batteries in practical applications.</p>