While investigating the ternary Cu-Zn-Sb system, a ternary phase Cu6Zn2Sb2 was first identified by D. Minić et al. , later it was structurally characterized by Misra et. al. According to their reports, it adopts the TiAl3Ge structure type [P4/nmm, tP10, 129] . The 10 atoms in the unit cell are distributed among four independent crystallographic sites, with the neighbouring Cu and Zn being perfectly ordered in nature. While investigating the homogeneity range of Cu6Zn2Sb2, two different compositions were further explored, i.e. Cu5.5 Zn2.5Sb2 and Cu5Zn3Sb2, where Zn selectively chooses one of the two different Cu-sites of Cu6Zn2Sb2. The site preference of Zn was established by the combinations of X-ray, neutron diffraction, and first-principle total energy calculations .