AbstractThe novel potassium sulfido cobaltate, K2[Co3S4] is introduced, with 25% vacancies of the cobalt positions within a layered anionic sublattice. The impedance and dielectric investigations indicate a remarkable ionic conductivity of 21.4 mS cm−1 at room temperature, which is in the range of highest ever reported values for potassium‐ions, as well as a high electrical permittivity of 2650 at 1 kHz, respectively. Magnetometry results indicate an antiferromagnetic structure with giant intrinsic exchange bias fields of 0.432 and 0.161 T at 3 and 20 K respectively, potentially induced by a combination of the interfacial effect of combined magnetic anionic and nonmagnetic cationic sublattices, as well as partial spin canting. The stability of the exchange bias behavior is confirmed by a training effect of less than 18% upon 10 hysteresis cycles. The semiconductivity of the material is determined, both experimentally and theoretically, with a bandgap energy of 1.68 eV. The findings render this material as a promising candidate for both, active electrode material in potassium‐ion batteries, and for spintronic applications.