Intermetallic FeSb2 and CrSb2 and their nanocomposites (FeSb2/C and Sb/Cr3C2/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 FeSb2 and CrSb2 was investigated using ex situ X-ray diffraction and high resolution transmission electron microscopy. The FeSb2/C and Sb/Cr3C2/C nanocomposite electrodes exhibited greatly enhanced electrochemical behaviors compared to the FeSb2 and CrSb2 electrodes. Additionally, the Sb/Cr3C2/C nanocomposite electrode showed a better electrochemical performance than the FeSb2/C nanocomposite electrode.