Abstract Raman spectra have been measured for ZnCl 2 ZnX 2 and ZnCl 2 KX (X = Br, I) glasses to investigate the structure of the glasses with varying composition. The assignment of each band was made, and the change of the spectra with composition was explained in terms of the bridging and non-bridging states of halide ions and the change of the tetrahedral units, ZnX n Cl 4− n 2− ( n = 0–4), formed in the glasses. As the content of ZnX 2 in ZnCl 2 ZnX 2 glasses increases (20 → 80 mol%), the peak frequency of the ZnCl stretching mode increases (238 → 248 cm −1 in X = I glasses, 238 → 259 cm −1 in X = Br glasses) while the ZnI and ZnBr stretching frequencies decrease (173 → 120 cm −1 for ZnI, 196 → 157 cm −1 for ZnBr). The decrease of the ZnI and ZnBr band frequencies was attributed to the increase of the number n of the ZnX n Cl 4− n 2− tetrahedra. The increase of the ZnCl frequency suggests the existence of the bonding state of Cl − ions which is intermediate between the bridging and the non-bridging states. In ZnCl 2 KX glasses, the ZnCl non-bridging band at about 300 cm −1 was observed in addition to the bands observed in ZnCl 2 ZnX 2 glasses. The addition of KX produces non-bridging anions while the tetrahedral units, ZnX n Cl 4− n 2− are also formed.