All-solid-state sodium batteries are attractive due to the abundance of sodium and advantageous for safe battery operation by avoiding flammable organics and liquids and suppressed dendrite formation. Currently, the lack of a chemically stable sodium solid electrolyte with high ion conductivity at room temperature is one of the challenges for future development of sodium batteries. Herein, we present a NaxCoO2/Nasicon/Na thin-film model sodium solid-state battery using a Sc-substituted Nasicon solid electrolyte with a high ionic conductivity of 4 × 10−3 S cm−1. The battery shows a high specific capacity of 150 mAh g−1 at room-temperature and discharge rates of up to 6C. Excellent chemical stability of this solid electrolyte at high voltages of up to 4.2 V increases the accessible sodium (de)intercalation range and battery capacity. Direct extraction of the interface resistances between the electrode materials of the thin-film model cell using electrochemical impedance spectroscopy gives a unique opportunity of correlation the electrochemical performance with properties of electrode materials and their interfaces.