A method is presented to determine the photoelectron surface core-level shift (SCLS) of 3d transition metals using x-ray photoelectron spectroscopy. The experimental difficulties arising from the relatively large broadening of photoemission lines in the 3d transition series can be overcome by the analysis of the angular dependence of photoemission spectra. The proposed method has been demonstrated using well-defined single-crystal surfaces of copper. The observed values of the SCLS for copper are compared with those predicted by both ab initio calculations and a macroscopic atom model. The experimental determination of SCLSs opens alternative routes for collecting thermochemical data for surfaces/interfaces.