Heavy-alkali post-deposition treatments (PDTs) utilizing Cs or Rb has become an indispensable step in producing high-performance Cu(In,Ga)Se2 (CIGS) solar cells. However, full understanding of the mechanism behind the improvements of device performance by heavy-alkali treatments, particularly in terms of potential modification of defect characteristics, has not been reached yet. Here, we present an extensive study on the effects of CsF-PDT on material properties of CIGS absorbers and the performance of the final solar devices. Incorporation of an optimized concentration of Cs into CIGS resulted in a significant improvement of the device efficiency from 15.9 to 18.4% mainly due to an increase in the open-circuit voltage by 50 mV. Strong segregation of Cs at the front and rear interfaces as well as along grain boundaries of CIGS was observed via high-resolution chemical analysis such as atomic probe tomography. The study of defect chemistry using photoluminescence and capacitance-based measurements revealed that both deep-level donor-like defects such as VSe and InCu and deep-level acceptor-like defects such as VIn or CuIn are passivated by CsF-PDT, which contribute to an increased hole concentration. Additionally, it was found that CsF-PDT induces a slight change in the energetics of VCu, the most dominant point defect that is responsible for the p-type conductivity of CIGS.