In situ solvothermally synthesized composite (SSC) and mechanically blended composite (MBC) of nanosized CoSb3 and multiwalled carbon nanotubes (MWNTs) were prepared and investigated as potential anode materials for Li-ion batteries. It was found that SSC exhibits an entanglement structure of nanosized CoSb3 and MWNTs and shows significantly better cycling stability than MBC. The reversible capacity of SSC electrode reaches 312mAhg−1 at the first cycle and remains above 265mAhg−1 after 30 cycles.