Developing K-ion conducting solid-state electrolytes (SSEs) plays a critical role in the safe implementation of potassium batteries. In this work, we report a chalcogenide-based potassium ion SSEs, K 3 SbSe 4 , which adopts a trigonal structure at room temperature. Single-crystal structural analysis reveals a trigonal-to-cubic phase transition at the low temperature of 50°C, which is the lowest among similar compounds and thus provides easy access to the cubic phase. The substitution of barium for potassium in K 3 SbSe 4 leads to the creation of potassium vacancies, expansion of lattice parameters, and a transformation from a trigonal phase to a cubic phase. As a result, the maximum conductivity of K 3-2x Ba x SbSe 4 reaches around 0.1 mS/cm at 40°C for K 2.2 Ba 0.4 SbSe 4 , which is over two orders of magnitude higher than that of undoped K 3 SbSe 4 . This novel SSE is successfully employed in a K-O 2 battery operating at room temperature where a polymer-laminated K 2.2 Ba 0.4 SbSe 4 pellet serves as a separator between the oxygen cathode and the potassium metal anode. Effective protection of the K metal anode against corrosion caused by O 2 has been demonstrated. This article is protected by copyright. All rights reserved.