We report the electrochem. study of Ti-Sn-Sb alloy (TiSnSb) towards Li, as an anode for Li-ion batteries. TiSnSb can reversibly take up more than 5 lithium atoms per formula unit leading to reversible capacities of 540 mA-h/g and 4070 mA-h/cm3 at 2C rate. From complementary operando x-ray diffraction and Moessbauer spectroscopy measurements, it was shown that during the first discharge the TiSnSb undergoes a conversion process leading simultaneously to the formation of Li-Sb and Li-Sn alloys. At the end of the discharge, Li3Sb and Li7Sn2 were identified. Once the first discharge is achieved, both phases were shown to form Ti-Sn or Ti-Sb or Ti-Sn-Sb nanocomposites. The cycling performance of TiSnSb was shown to be excellent with maintaining 90% of the sp. capacity during 60 cycles at 2C rate. The good electrochem. performance of TiSnSb (compared to Sn and Sb) seems to be a consequence of the presence of the non-active metal. The comparative study of Ti/Sn/Sb composite demonstrated that the structural feature of the pristine material clearly impacts both the mechanism involved during the cycling and the corresponding performance. [on SciFinder(R)]