Three different types of HT-LiCoO2/lithium lanthanum titanate (LLT) assemblies were produced by depositing an HT-LiCoO2 cathode on polycrystalline LLT with various surface finishes, to investigate the effects of the HT-LiCoO2/LLT interface structure on the electrochemical properties of the assemblies. An amorphous layer is confirmed to he introduced by Ar ion irradiation to crystalline LLT. The HT-LiCoO2/LLT assembly composed of the ion-irradiated LLT exhibits good cycle stability and relatively low apparent interface resistivity. These results indicate that the introduction of an amorphous LLT layer by surface modification of crystalline LLT is very effective in improving the structural stability and lithium-ion conductivity of the interface between HT-LiCoO2 and crystalline LLT.