Lithium insertion mechanism in some antimony-based compounds: SnSb, CoSb3, CrSb2, TiSb2 has been studied by means of 121 Sb Mössbauer spectrometry which gives valuable information about the local electronic structure of the probed element (Sb). The structural and electronic modifications induced by insertion of lithium have been characterized. For these Sb-based materials the lithium insertion mechanisms involve Li3Sb formation and composite multi-phase separations with one component displaced from the pristine compound.