Interfacial resistance at electrode‐high Li+ conductive solid electrolytes must be reduced well to develop high‐power all‐solid‐state batteries using oxide‐based solid electrolytes (Ox‐SSBs). Herein, crystalline electrode films of LiCoO2 (LCO) are formed on a high Li+ conductive crystalline‐glass solid electrolyte sheet, Li1.3Al0.3Ti2(PO4)3 (LATP) (σ25 °C = 1 × 10−4 S cm−1), at room temperature by aerosol deposition (AD), and the effects of the annealing temperature on the interfacial resistivities (Rint) at the LCO/LATP are investigated. The Rint visibly increases by annealing over 500 °C with the growth of Co3O4 as a reactant. In contrast, Rint is reduced to ≈100 Ω cm2 by low‐temperature annealing at 250–350 °C due to superior contact through the structural rearrangement of an artificial metastable interface formed by the AD. These results are applied to bulk‐type Ox‐SSB, Li/Li7La3Zr2O12(LLZ)/LCO–LATP, and our best Ox‐SSB delivers a discharge capacity of 100 mA cm−2 at 100 °C.