Intermetallic FeSb 2 and CrSb 2 and their nanocomposites (FeSb 2 /C and Sb/Cr 3 C 2 /C) were prepared using solid-state routes, such as heat-treatment and high-energy mechanical milling, in order to enhance the electrochemical properties of Sb. These electrodes were tested as anode materials for rechargeable Li-ion batteries. The reaction mechanism of intermetallic FeSb 2 and CrSb 2 was investigated using ex situ X-ray diffraction and high resolution transmission electron microscopy. The FeSb 2 /C and Sb/Cr 3 C 2 /C nanocomposite electrodes exhibited greatly enhanced electrochemical behaviors compared to the FeSb 2 and CrSb 2 electrodes. Additionally, the Sb/Cr 3 C 2 /C nanocomposite electrode showed a better electrochemical performance than the FeSb 2 /C nanocomposite electrode.