Calcium zinc oxysulfide (CaZnOS) and cognate semiconductors are emerging materials possessing exceptional piezoluminescent properties. A CaZnOS:ZnS binary heterocompound doped with various Mn ²⁺ concentrations from 0.1 to 8% has been prepared using the solid-state reaction method. The structural, chemical and optical properties of the obtained powders are studied. Their crystal structure and compositional analyses have shown two stable main phases of ZnS and CaZnOS so that the powder generally appears as a binary compound of the ZnS:Mn ²⁺ and CaZnOS:Mn ²⁺ particles. The role of ZnS:Mn ²⁺ and CaZnOS:Mn ²⁺ phases on mechanoluminescence (ML) and photoluminescence (PL) is particularly investigated. The luminescence spectra show the contribution of ZnS:Mn ²⁺ and CaZnOS:Mn ²⁺ as particles of yellow and red colors, respectively. When increasing the Mn ²⁺ concentration, a redshift …