The solubility of sphalerite (ZnS) was measured in KCl-HCl-H₂O solutions at 300–600°C and 0.5–2.0 kbar. The silicate assemblage K-feldspar-muscovite (or andalusite)-quartz was used to buffer the solution to acid conditions, resulting in the total solubility reaction 2K⁺ + KAl₂AlSi₃O₁₀(OH)₂ + 6SiO₂ + ZnS + nCl⁻ = ZnCl_n⁽²⁻ⁿ⁾ + 3KAlSi₃O₈ + H₂S. (muscovite) (quartz) (sphalerite) (K-feldspar) A computer retrieval technique was used to derive average chloride ligand numbers for chlorozinc species at 0.25–2.0 molal total chloride. This technique mathematically solves for the average ligand number using a series of pertinent chemical relations at P and T. Mono- and di-chlorozinc species were found to predominate throughout the pressure-temperature-composition range investigated. The logarithms of the first and second dissociation constants for ZnCl₂⁰ were evaluated over the P-T range; for example, at 1 kbar, the values −0.41 and −1.42 were computed for the logarithm of the first dissociation constant, while −7.62 and −10.57 were computed for the logarithm of the second dissociation constant, for 400 and 500°C, respectively. Results are compared to past studies conducted at subcritical conditions and differ in that we find no evidence for more highly coordinated chloro-zinc species except possibly for ZnCl₃⁻ at 600°C, 1 and 2 kbar. Our results are consistent with electrostatic theory, which favors lower charged to neutral molecules in low dielectric-constant media.