The local atomic structures of liquid Sb 40S 60, Sb 44Sb 56 and Sb 90S 10 were investigated by the neutron diffraction method. The characteristic features of the structure factor, S( q), of liquid Sb 40S 60 are as follows: (i) a prepeak is observed at around q=1.2 Å −1, (ii) heights of the first and second peaks in S( q) are similar, (iii) oscillations in S( q) are persisted over the 25 Å −1. The overall feature of S( q) for liquid Sb 44S 56 is similar to that for liquid Sb 40S 60. On the other hand, the feature of S( q) for liquid Sb 90S 10 is quite different from those of liquid Sb 40S 60 and Sb 44S 56. The prepeak is not observed in S( q) for liquid Sb 90S 10 while oscillation of S( q) still remains over 20 Å −1. The height of the first peak in S( q) becomes larger than that of the second peak. These results suggest that there exists the short-range order for these liquid Sb–S mixtures and also exists the middle-range order in the liquid Sb 40S 60 and Sb 44S 56. The local atomic structure of liquid Sb 90S 10 seems to be quite different from that of liquid Sb 40S 60, which can be related to the metal–non-metal transition and the existence of the two-phase region between the composition of Sb 40S 60 and Sb.