The 80SnS·20P2S5 (mol%) amorphous material was prepared by a mechanical milling technique. The obtained material was fine powders with a few micrometers in size. All-solid-state cells with the SnS–P2S5 amorphous electrode and the Li2S–P2S5 glass-ceramic electrolyte, where a continuous P2S5 sulfide network between both the materials was formed, were fabricated. The cells exhibited high reversible capacity of over 400mAhg−1 for 50 cycles at room temperature. The addition of P2S5 as a glass former to SnS improved cell capacity and cyclability, suggesting that P2S5 network played an important role in enhancing the availability of SnS as an electrode material.