Graphene-like and platelike WS2 were obtained by solid-state reactions. High-resolution (HR) TEM, BET, and Raman scattering studies show that the graphene-like WS2 is a few-layer-structured material. It exhibits better electrochemical performances than the platelike WS2. Structural characterization indicates that metallic W and Li2S are the end products of discharge (0.01 V versus Li+/Li), whereas metallic W and S are the recharge (3.00 V) products. In addition, X-ray absorption near-edge structure (XANES) characterization shows that the d electrons of W deviate towards the Li (or S) atom during the discharge/charge process, thus forming a weak bond between W and Li2S (or S).