Lithium ion conducting thin film electrolytes, Li2O-B2O3-P2O5 glass systems, were prepared with a wide range of chemical composition by co-sputtering method with multi-targets. The maximum ionic conductivity at room temperature was 1.22 x 10(-6) S/cm and the activation energy of this specimen was 0.54 eV when enhanced by the mixed former effect and the high network modifier content. The increased ion conductivity of the films appeared to be associated with the formation of stable tetrahedral borate at high lithium concentration and this structural change facilitated faster ion migrations. The relationship between the glass structure and electrical performance of the mixed former glasses was investigated by the infrared spectra analysis of borate networks. The conductivity of the mixed former electrolytes increased gradually with increasing the RF power on Li2O target, and the maximum conductivity was obtained at 100W. The structural role of the network modifier in xLi(2)O-(1-x)(B2O3-P2O5) glasses was analyzed by the O1s spectra of X-ray Photoelectron Spectroscopy. A quantitative deconvolution of O1s spectra suggests that the increased conductivity with increasing lithium content is due to the formation of non-bridging oxygen. (C) 2012 Elsevier B.V. All rights reserved.