Amorphous Li2O–B2O3–P2O5 films were fabricated using “aerosol flame deposition (AFD)” method for the thin film battery application. The liquid or gas type precursor sources such as Li precursor solutions, BCl3 and POCl3 were used to fabricate the electrolyte films. In this work, we studied the effect of P2O5 in a LiO2–P2O5–B2O3 system formed at various flow rates of POCl3. XRD analysis revealed that the crystalline phase of H3BO3 as well as other oxides was formed in glass soot. As the flow rate of POCl3 increased, the glass soot gradually changed to amorphous phase. The ionic conductivity of the soot was measured and the FT-IR and Raman spectroscopy were used to correlate the measured conductivity to the glass network structure in the deposited soot film. The maximum conductivity of electrolyte prepared at conditions of 20sccm flow rate of BCl3 and 80sccm flow rate of POCl3 was 2×10−6 at room temperature. As P2O5 contents increased, the conductivity of glass electrolyte increased due to the increase of PO structural unit associated with non-bridging oxygens (NBO).