All-solid-state batteries (ASSBs) represent a promising battery strategy to achieve high energy density with great safety. However, inadequate kinetic property and poor interfacial compatibility remain great challenges, which impede their practical application. A prototype of dual-ion conductor of Li + synchronized with Cu + unlocks a four-electron redox reaction with high reversibility and fast kinetics. As a result, the constructed ASSB exhibited a high reversible capacity of 603.0 mA·hour g −1 and an excellent cycling retention of 93.2% over 1500 cycles. Moreover, because of the ion highway connecting active materials and catholytes constructed by dual-ion conductor, remarkable temperature tolerance (−60°C) and excellent rate performance (231.6 mA·hour g −1 at 20 mA cm −2 ) were achieved. The superior electrochemical performance can be ascribed to the migration pathway with small energy barrier and low tortuosity once the Cu + introduced into Li 6 PS 5 Cl. This work creates a unique perspective of ASSBs with dual-ion conducting strategy, thus inspiring a potential developing strategy of state-of-the-art ASSBs.