The core-level S 2p and Pb 5d spectra of galena (natural PbS) single crystals have been investigated using synchrotron radiation. Comparison between a synthetic PbS and a mineral galena has been made and the former gave broader S 2p lines than the latter. In both samples a strong broadening of the line was observed when the temperature was increased. Also, the surface core-level shift (SCLS) was slightly smaller for the synthetic sample. No shift was found for the Pb 5d lines. The atomic force microscopy (AFM) study of the mineral (100) surface showed that only one type of atom (most likely sulphur) is visible, in agreement with Heinzelmann et al. Copyright (C) 2002 John Wiley Sons, Ltd.