X-ray and femtosecond UV photoelectron spectroscopy, secondary ion mass spectrometry and photoluminescence imaging were used to investigate the electronic and elemental properties of the CZTS,Se surface and its oxides. Oxide removal reveals a very Cu poor and Zn rich surface relative to bulk composition. O and Na are observed at the surface and throughout the bulk. Upward bending of the valence bands indicates the presence of negative charge in the surface region and the Fermi level is found near the band gap center. The presence of point defects and the impact of these findings on grain boundary properties will be described. © 2014 AIP Publishing LLC.