The results of single crystal X-ray investigations of the quasi-ternary channel compounds TlCr 5 S 8±y Se y (1 ≤ y ≤ 7) show a linear increase of the unit cell volume with increasing Se content as expected for a solid solution. The successive occupation of the four distinct chalcogene sites by Se, however occurs in a nonlinear way. During the substitution the two sites X1 and X2 are strongly preferred by the Se atoms. For site X3 no significant preference is observed and site X4 is clearly less favoured by the Se atoms. This unusual behaviour can be interpreted on the basis of the different polarizabilities of the constituting atoms. The occupation of X1 and X2 by Se gives the strongest covalent bonding interactions, especially between Tl and Se thus being the driving force for the high preference of Se for these two sites. The preferential occupation of the four crys-tallographically independent chalcogene sites leads to an unexpected and spectacular dependence of the unit cell parameters and of the interatomic distances as function of the Se content. The a axis shows a negative deviation from linearity, whereas the c axis exhibits a positive one. The monoclinic angle b passes a maximum at y = 5, and finally drops to a value comparable with that obtained for the pure sulfide. A detailed analysis demonstrates that the series can be divided into the two different regions 0 ≤ y ≤ 4 and 5 ≤ y ≤ 8, both characterized by a linear variation of the lattice parameters as well as of the interatomic distances.