The following article appeared in Journal of Applied Physics 111.3 (2012): 034903 and may be found at http://scitation.aip.org/content/aip/journal/jap/111/3/10.1063/1.3679604Na has deliberately been incorporated into Cu(In,Ga)Se2 (CIGSe) chalcopyrite thin-film solar cell absorbers deposited on Mo-coated polyimide flexible substrates by adding differently thick layers of NaF in-between CIGSe absorber and Mo back contact. The impact of Na on the chemical and electronic surface structure of CIGSe absorbers with various Cu-contents deposited at comparatively low temperature (420 C) has been studied using x-ray photoelectron and x-ray excited Auger electron spectroscopy. We observe a higher Na surface content for the Cu-richer CIGSe samples and can distinguish between two different chemical Na environments, best described as selenide-like and oxidized Na species, respectively. Furthermore, we find a Cu-poor surface composition of the CIGSe samples independent of Na content and - for very high Na contents - indications for the formation of a (Cu,Na)-(In,Ga)-Se like compound. With increasing Na surface content, also a shift of the photoemission lines to lower binding energies could be identified, which we interpret as a reduction of the downward band bending toward the CIGSe surface explained by the Na-induced elimination of In Cu defects.X.S., R.F., D.G., R.G.W., and M.B. are grateful to the Helmholtz-Association for financial support (VH-NG-423). R.F. also acknowledges the support by the German Academic Exchange Agency (DAAD; 331 4 04 002)