Abstract High ionic conductivity at reduced temperatures may allow electrochemical cell applications to be efficiently scaled up. Herein, we introduce an approach that exploits electrode-electrode synergy and in situ structural transformation to increase the ionic conductivity of an electrolyte within the electrochemical cell. This transformation is based on the formation of a Li2TiO3-Li2CO3 heterostructure electrolyte via the combination of a TiO2 semiconductor precursor, polystyrene spheres as the soft skeleton, and the lithium-based electrode LiNi0.8Co0.15Al0.05O2. The unique surface and interface of the heterostructure electrolyte enable the formation of long-range ion transport channels that lower electrode impedance, resulting in a superior ionic conductivity of 0.23 S cm−1 at 550 °C and a high-power density of 1239 mW cm−2. Our general method to form superionic electrolytes shows potential in fuel cell technologies.