Photoemission microspectroscopy on the layered misfit compound (PbS)1.13TaS2 provides direct evidence for Ta substitution into PbS layers as well as for Pb substitution into TaS2 layers. This metal cross substitution alters the charge balance between alternating layers and can explain the remarkable stability of (PbS)1.13TaS2 and, possibly, of analogous misfit compounds. It is suggested that even formally stoichiometric misfit compounds can be stabilized by this mechanism.