Abstract Two key strategies for enhancing the efficiency of Cu(In,Ga)Se 2 solar cells are the bandgap gradient across the absorber and the incorporation of alkali atoms. The combined incorporation of Na and Rb into the absorber has brought large efficiency gains compared to Na‐containing or alkali‐free layers. Here, transient absorption spectroscopy is employed to study the effect of NaF or combined NaF+RbF postdeposition treatments (PDT) on minority carrier dynamics in different excitation volumes of typical composition‐graded Cu(In,Ga)Se 2 solar cells. Electron lifetimes are found to be highly dependent on the film composition and morphology, varying from tens of nanoseconds in the energy notch to only ≈100 ps in the Ga‐rich region near the Mo‐back contact. NaF PDT improves recombination lifetimes by a factor of 2–2.5 in all regions of the absorber, whereas the effectiveness of the RbF PDT is found to decrease for higher Ga‐concentrations. Electron mobility measured in the absorber region with large grains is promoted by both alkali PDTs. The data suggest that NaF PDT passivates shallow defect states (Urbach tail) throughout the Cu(In,Ga)Se 2 film (including the interior of large grains), whereas the additional RbF PDT is effective at grain boundary surfaces (predominantly in regions with medium to low Ga‐concentrations).