Novel hybrid solid electrolytes were prepared by mechanochemistry using the Li+ conductive Li2S–P2S5 glasses and –OH terminated oligomers. The P–O–C bonds were observed in FT-IR spectra for the obtained electrolytes, suggesting that the molecular level hybrid materials were synthesized. The addition of small amounts of oligomers into the glass successfully enhanced the conductivity of hybrid electrolytes by lowering glass transition temperature. The hybrid electrolyte with 2mol% of 1,4-butanediol exhibited the ambient temperature conductivity of 9.7×10−5 Scm−1, which is 1.5 times as large as the conductivity of the pristine glass. The hybrid with a polyether showed lower conductivity than the hybrid with 1,4-butanediol. Incorporating oligomer blocks into glass network is a new approach to enhance the conductivity of glass-based solid electrolytes.