High lithium ion conducting glasses were successfully prepared in the Li2S-based sulfide and oxysulfide systems with a wide range of compositions by a mechanochemical procedure. The properties and structure of these glasses were similar to those of corresponding melt-quenched glasses. Highly conductive glass-ceramics were also obtained by a heat treatment of the obtained glasses. The glass-ceramics mainly composed of the crystal analogous to the highly conductive thio-LISICON II phase in the system Li4-xGe1-xPxS4 showed conductivity as high as 10(-3) S cm(-1). All-solid-state batteries using the Li2S-based glasses and glass-ceramics were constructed in order to evaluate the cell performance as a lithium secondary battery. The cell In/80Li(2)S.20P(2)S(5) (mol.%) glass-ceramic/LiCoO2, exhibited excellent cycling performance of over 200 times with no decrease in the charge-discharge capacity (100 mA h g(-1)).