The different surface reconstructions of the 3C-SiC(001) surface have been systematically studied by high-resolution core-level photoelectron spectroscopy. For the Si-rich 3×2 surface, three different Si 2p surface components are clearly identified supporting the structure model with 2 3 ML of Si ad-dimers. It is confirmed that the c(2×2) and 2×1 surfaces are respectively C- and Si-terminated by observing a single dominant surface component in the C 1s or Si 2p spectra with binding energy shifts of 1.04 eV and −0.50 eV respectively relative to the bulk component. The atomic origins of these surface core levels are assigned and the core-level shifts are compared with previous measurements and recent theoretical calculations.