The suitability of silver sulfide (Ag2S) and its nanocomposite Ag2S/C, prepared by simple solid-state synthetic routes such as high-energy mechanical milling and heat treatment, for use as anode materials in rechargeable Li-ion batteries has been investigated. A well-developed Ag2S phase is identified from X-ray diffraction (XRD) patterns, and XRD and high-resolution transmission electron microscopy observations confirm that Ag2S nanocrystallites in Ag2S/C are uniformly distributed within an amorphous carbon matrix. The electrochemical reaction mechanism of Ag2S with Li is identified by ex situ XRD analyses of an Ag2S/C nanocomposite electrode. The Ag2S/C nanocomposite anode shows good cycling behavior and a high capacity of about 430mAhg−1 after 100cycles.