Either metallic Na or NaF were deposited onto Cu(In, Ga)Se-2 surfaces and studied by photoelectron spectroscopy and surface photovoltage spectroscopy without breaking the ultra-high vacuum. The deposition of elemental Na at room temperature led to the formation of an intermediate Cu and Ga rich layer at the CIGSe surface, whereas for NaF the composition of the CIGSe surface remained unchanged. A metal like surface induced by an inverted near surface region with a reduced number of defect states was formed after the deposition of Na. Under the chosen experimental conditions, the near surface layer was independent on the amount of Na and stable in time. In contrast, the usage of NaF weakened the inversion and led to an increased band bending compared to the untreated CIGSe sample. The SPV signals decreased with proceeding time after the deposition of NaF. (C) 2018 Elsevier B.V. All rights reserved.