Infrared chemiluminescence studies of the bimolecular reactions H + S2Cl2, H + SOCl2, and H + SCl2 were carried out in order to explore the primary vibrational‐rotational distributions of the excited product molecule HCl. Assuming no formation of HCl(v′ = 0) in the case of the reactions H + SOCl2 and S2Cl2 at least 38%, respectively 32% of the available energy enter vibration and rotation of the newly formed HCl molecule. In contrast for the reaction H + SCl2 more than 56% of the available energy are transferred to the internal degrees of freedom of HCl. The bimodal rotational distribution of the HCl formed by H + SCl2 reported previously [4] was confirmed.