Mn-doped ZnO–ZnS complex nanocrystals were fabricated through coating of dodecanethiol on Mn-doped ZnO nanocrystals. The relationship between the component of white light emission and the coordination environments of Mn-dopants were experimentally investigated. It was shown that Mn ions mainly formed Mn³⁺O₆ octahedra in as prepared Mn-doped ZnO, while the Mn³⁺ ions on the surface of ZnO transferred into Mn²⁺ ions at the interface between ZnO and ZnS after dodecanethiol coating. The Mn²⁺S₄ tetrahedron density and the orange emission intensity increased upon enhancing the dodecanethiol content. These results provide an alternative way to optimize the white emission spectrum from nanocrystals of Mn-doped ZnS–ZnO complex structures through modulation of the coordination environment of Mn ions.