TiSb2 is Khatyrkite structured and crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Ti4+ is bonded in a 8-coordinate geometry to eight equivalent Sb2- atoms. All Ti–Sb bond lengths are 2.94 Å. Sb2- is bonded in a 5-coordinate geometry to four equivalent Ti4+ and one Sb2- atom. The Sb–Sb bond length is 2.91 Å.