Experimental studies and characterization of the interfacial impedance of a novel solvent-casted solid polymer electrolyte (SPE) and Li1.3Al0.3Ti1.7(PO4)3 (LATP) ceramic bilayer electrolyte are conducted. Overall, resistance of the bilayer electrolyte decreased compared to single LATP ceramic electrolyte. The mechanism of the enhanced ion transportation at the interface is analyzed and discussed. Using the as-prepared multilayer electrolyte, all-solid-state lithium ion batteries (ASSLIBs) were fabricated with lithium metal as anode and LiMn2O4 (LMO) as cathode material. The charge/discharge properties and impedance of the cell at different temperatures were investigated. This work demonstrates the feasibility and potential of using a multilayer electrolyte structure for ASSLIBs with flexible geometries and dimensions for design.