Liquid chalcogen-halogen A 2 X 2 (A: S, Se, X: Cl, Br) is a racemic mixture of enantiomers between left-handed (L) and right-handed (D) chiral molecules. The lone-pair orbital of the chalcogen atom significantly affects the molecular conformation and intermolecular interaction. The latter depends on the size of the orbital and number density. High-energy X-ray diffraction measurements and reverse Monte Carlo (RMC) structural modelling were performed for liquid S 2 Cl 2 in addition to the previous structural analysis for liquid Se 2 Br 2 . By comparing the structures of the RMC model and hard-sphere Monte Carlo (HSMC) model, the effect of refinement on the experimental structure factor can be analysed. In this paper, nearest-neighbour intermolecular pairs are classified in terms of enantiomer pairs such as like-pair (L-L and D-D) and unlike-pair (L-D). As a result, the effect of a strong intermolecular attractive interaction is detected in Se 2 Br 2 as increasing the number of like-pairs with geometrical advantages from HSMC to RMC, whereas that of an intermolecular repulsive interaction is observed in S 2 Cl 2 as elongation of the averaged intermolecular S-S distance from HSMC to RMC. These results are consistent with the results of the ab initio molecular dynamics simulation for Se 2 Cl 2 and S 2 Cl 2 .