Black phosphorus was prepared from red phosphorus by using mixer mill and planetary ball-mill apparatuses. The composites with black phosphorus and acetylene black (AB) were also prepared by using the mixer mill apparatus. The mechanical milling of black phosphorus and AB brought about a decrease in size of secondary particles of the composites. The all-solid-state lithium cells with the composite and the Li2S–P2S5 glass-ceramic electrolyte exhibited the first discharge capacity of 1962mAhg−1 and the coulombic efficiency of 89% at the current density of 0.064mAcm−2 (24mAg−1). The all-solid-state cells worked at 3.8mAcm−2 (1.47Ag−1) at 25°C and showed the excellent cycle performance with a high capacity of over 500mAhg−1 for 150 cycles. Black phosphorus is one of the most attractive negative electrodes with both high capacity and high-rate performance in all-solid-state lithium rechargeable batteries with sulfide electrolytes.