Polycrystalline powders of the layered MnPS3 compound have been intercalated with K+ ions by ion-exchange to yield the K2xMn1-xPS3 intercalate. X-ray photoelectron spectroscopy has been applied to learn about the electronic structure of this compound. In particular, we have studied the XPS spectra of the Mn 2p and 3p, P and S 2p, K 2p and 3p core levels and of the valence band region. The binding energies for various core levels of the elements present in this compound and their observed chemical shifts are analyzed. The data give evidence for the lack of non-equivalent atoms of K, Mn, P and S. Shake-up satellites are present at the Mn 2p and 3p core levels. The occurrence of such lines allows us to hypothesize that K2xMn1-xPS3 is a large-gap insulating Mn compound. Confirmation that only an ion transfer accompanies the intercalation process is given from both the strong observed similarity with the corresponding XPS spectra in MnPS3 and the observed binding energy positions of the K 2p and 3p levels. As regards the valence band XPS spectrum, the observed analogies with the corresponding XPS spectra of the pure compound and of other K compounds have allowed us to single out two regions and their probable contributors. (c) 2005 Elsevier B.V. All rights reserved.