ZnS:Mn nanoribbons and ZnS:Mn,Eu triangular nanoprisms grown by thermal evaporation of ZnS powder mixtures containing MnCl2, and MnCl2 + EuCl3 powders respectively were investigated using X‐ray excited optical luminescence (XEOL) together with X‐ray absorption fine structure spectroscopy (XAFS) in total electron yield (TEY) and wavelength selected photoluminescence yield (PLY). XEOL and XAFS measurements were performed by tuning the X‐rays to the Zn, and Mn L2,3‐edge absorption regions, selectively exciting the respective elements. The dominant emissions resulted from the characteristic 4T1 − 6A1 transitions of the Mn2+ ion (576 nm) in the ZnS:Mn nanoribbons and ZnS:Mn,Eu nanoprisms. The results provide insight into the energy transfer mechanisms that occur and how they affect the overall luminescence of the Mn doped ZnS nanostructures.