In this work the Mn influence on X-ray photoelectron Zn 2p and S 2p spectra of ZnS thin films with low Mn concentration have been studied. The careful analysis of Zn 2p and S 2p spectra shows that the Mn impurity in concentration less than sensitivity limit of XPS leads to the decreasing binding energy for Zn 2p electrons on 0.3 eV and for S 2p electrons on 0.6 eV. It was explained by elementary Zn clusters formation for similar to 7 at.% of Zn atoms and by changing the Zn-S-Zn groups on the Mn-S-Mn groups for similar to 5 at.% of S atoms.