(100-x) (0.78Li2S·0.22P2S5)·xLi3BO3 (0 ≤ x ≤ 5) solid electrolytes are prepared via mechanical milling and a post heat-treatment process, and the resulting electrochemical properties are investigated in conjunction with structural analysis. Adding of Li3BO3 into the (100-x) (0.78Li2S·0.22P2S5)·xLi3BO3 solid electrolyte is expected to enhance the conductivity and lower the activation energy as a consequence of changing the structural unit in the glass network. It turned out that the doping of Li3BO3 enhances the conductivity by enlarging the glass forming region and promoting precipitation of high lithium ion conductive thio-LISICON II analog. 97 (0.78Li2S·0.22P2S5)·3Li3BO3 (x = 3) glass-ceramics exhibits the highest conductivity (1.03 × 10−3 S cm−1). Structural analysis shows that the samples with Li3BO3 added to the electrolyte are composed of the main structural unit of PS4 3− with partially-modified structural unit of PO4 3−, which are believed to effectively enhance the conductivity and decrease the activation energy. In glass-ceramics produced from these materials, the thio-LISICON II phase with higher ionic conductivity tends to be stabilized by the addition of Li3BO3. Additionally, the formation of space-charge layer is relaxed by Li3BO3 doping. As a result, the all-solid-state cell shows high initial discharge capacity of 156 mAh g−1, and the capacity is retained to be 149 mAh g−1 for 40 cycles.