This study describes in detail the effects of sodium and potassium on Cu(In,Ga)Se2 (CIGS) absorbers and solar cells. We report on the influence of these species on the surface and bulk composition as well as bulk defect structure of CIGS films as revealed by X-ray photoelectron spectroscopy (XPS), secondary ion mass spectroscopy (SIMS), and photoluminescence (PL). From the XPS studies it is found that Na and K promote oxygen absorption onto the CIGS films. Furthermore, potassium accelerates the formation of indium and gallium oxides on the film surface, making the surface Cu-deficient. Low temperature PL studies suggest that (i) Na and K help passivate non-radiative recombination centers, presumably at the grain boundaries, and (ii) Na further impacts the bulk defect structure inside of CIGS grains, which is not observed with K. This change in bulk defect structure is attributed to the greater diffusivity of Na in CIGS relative to K due to the smaller atomic size. This in-depth study (integration of XPS, SIMS, PL, and device characteristics) reveals that the surface chemistry and the grain boundary passivation have stronger influences on the device performance than the bulk defect structure.