The lattice parameter of cubic chemical vapor deposited (CVD) ZnS with measured oxygen concentrations <0.6 at. % and hydrogen impurities of <0.015 at. % has been measured and found to vary between −0.10% and +0.09% relative to the reference lattice parameter (5.4093 Å) of oxygen-free cubic ZnS as reported in the literature. Defects other than substitutional O must be invoked to explain these observed volume changes. The structure and thermodynamic stability of a wide range of native and impurity induced defects in ZnS have been determined by ab initio calculations. Lattice contraction is caused by S-vacancies, substitutional O on S sites, Zn vacancies, H in S vacancies, peroxy defects, and dissociated water in S-vacancies. The lattice is expanded by interstitial H, H in Zn vacancies, dihydroxy defects, interstitial oxygen, Zn and [ZnHn] complexes (n = 1,…,4), interstitial Zn, and S2 dumbbells. Oxygen, though present, likely forms substitutional defects for sulfur resulting in lattice contraction rather than as interstitial oxygen resulting in lattice expansion. It is concluded based on measurement and calculations that excess zinc atoms either at anti-sites (i.e., Zn atoms on S-sites) or possibly as interstitial Zn are responsible for the relative increase of the lattice parameter of commercially produced CVD ZnS.