This study focuses on preparing a hybrid electrolyte, the combination of 90 wt% inorganic solid and 10 wt% organic liquid, for lithium based rechargeable batteries to illustrate the effect of electrode/electrolyte interfacing on electrochemical performance. The inorganic solid electrolyte selected is Li1.3Ti1.7Al0.3(PO4)3, and the Li-ion conducting organic liquid electrolyte selected is 1 M LiPF6 in EC:DEC. Because of the addition of Li-ion conducting liquid between the solid electrode and solid electrolyte, the hybrid electrolyte cell minimizes the ineffective solid-on-solid interfaces common in all-solid-state cells. It is also expected that using a liquid electrolyte at the point of contact between the solid electrolyte and the electrode will adjust for the volume change of the electrode during Li insertion/extraction. As a result, the electrochemical performance of the hybrid electrolyte cell is superior to that of a solid electrolyte cell and is also competitive to that of a pure liquid electrolyte coin cell. Another advantage of the hybrid electrolyte cell observed in this work is that this system behaves as a self-safety device when sudden, higher temperatures are applied.