In the current study, we prepared a LixLa₃Zr₂O12 ((Al, Ta) LLZO) powder doped with 0.2 mol of Al and Ta using the sol-gel method and subsequently used it to fabricate solid electrolyte pellets. In pellets with lithium content of 6.2 and 6.82 mol, a cubic phase and a lithium-deficient pyrochlore mixed-phase were respectively observed. However, when the lithium content was 8.06 mol, a lithium-excess phase was also observed. Meanwhile, at 7.44 mol lithium, the (Al, Ta) LLZO ceramic pellets showed a pure cubic garnet phase with no secondary phase. When lithium was added excessively, a non-granular morphology was observed at the (Al, Ta) LLZO fracture surface in which the grains were tightly bonded by the liquid phase formed during sintering. Nyquist plots of the pellets showed that the effect of grain boundaries was eliminated and the pellets exhibited a high lithium ion conductivity of 4.26 × 10-4 S/cm. Using spin coating and multi-step heat treatment, we deposited LiCoO₂ (LCO) thin films on (Al, Ta) LLZO pellets to form cathodes. There was no significant interdiffusion between the LCO cathode and (Al, Ta) LLZO solid electrolyte and morphological analysis indicted that a thin interfacial layer (~10 nm) was formed between the LCO and the electrolyte. Finally, we demonstrated an all-solid-state rechargeable battery in the form of a coin cell comprising of an LCO cathode, Li metal anode, and (Al, Ta) LLZO solid electrolyte, which could yield a discharge capacity of ~100 mAh/g.