AbstractAlkali post deposition treatments (PDTs) of Cu(In,Ga)Se₂ absorbers have boosted the power conversion efficiency (PCE) of the solar cell devices in the last years. A detailed model explaining how the PDTs impact the optoelectronic properties at the nanoscale is still lacking. Here, via various scanning probe techniques, X‐Ray photo‐electron spectroscopy and high resolution secondary ion mass spectroscopy it is shown that the RbF PDT treatments lead to a one to one exchange of Rb with Cu at the surface. This exchange takes place in the naturally occurring Cu‐depleted CIGSe surface, known as the ordered vacancy compound. A detailed comparison between samples with different PDTs after various cleaning procedures furthermore highlights the necessity to perform all the measurements on NH₄OH cleaning surfaces only. After NH₄OH, no RbInSe₂ phase could be detected at the surface anymore and the surface bandgap, as measured with scanning tunneling spectroscopy is only 1.7 eV. The findings demonstrate that the existence of a RbInSe₂ phase is most likely not responsible for the recent improvements in power conversion efficiency for state of the art solar cells. The primary effect of the PDT treatment is a modification of the ordered vacancy compound, where Cu is exchanged with Rb.