Ti 5 Sb 2 . 2 Se 0 . 8 was prepared by the annealing of mixtures of Ti, TiSe 2 and TiSb 2 in sealed Ta tubes under dynamic vacuum at 1200 o C. The partial substitution of Sb by Se in Ti 5 Sb 3 did not result in crystallization in a different structure type. However, the unit cell dimensions changed anisotropically from a=1021.73(5), b=832.81(5) and c=714.59(4) pm for Ti 5 Sb 3 to a=1022.2(1), b=821.0(1) and c=696.18(6) pm for Ti 5 Sb 2 . 2 0 2 ( 8 ) Se 0 . 7 9 8 (orthorhombic symmetry, space group Pnma, No. 62, with Z=4). The crystal structure (Yb 5 Sb 3 type) comprises a three-dimensionally extended network of Ti atoms that includes the main group atoms in three- and two-fold capped trigonal prismatic voids. The distortions are reflected in a shrunk (Sb,Se)Ti 8 polyhedron as well as in a shrunk SbTi 9 polyhedron with decreased Ti-Sb distances, occurring with to a minor extent decreased Ti-Ti distances as well. Extended Huckel band structure calculations reveal both compounds being metallic with stronger Ti-Sb and Ti-Ti bonding in the case of the Se containing phase.