We present here a complementary study on germanium doping of the wider-band-gap CuGaSe₂ (CGS) chalcopyrite. In photoluminescence studies, the occurrence of a new emission line was identified as Ge related and explained as a donor-acceptor-pair recombination. The precise role the Ge is playing in this doping of CGS is revealed by x-ray absorption spectroscopy and ab initio calculations based on the density-functional theory. Extended x-ray absorption fine-structure spectroscopy (EXAFS) as well as x-ray absorption near-edge spectroscopy performed at the GeK -, CuK -, and GaK -edge show that the Ge dopants occupy the cationic sites of Ge_Cu or Ge_Ga of the host lattice. The complementary ab initio calculations support the EXAFS results. They further indicate that the incorporated Ge atoms preferentially occupy Ga sites when relaxation around the dopant is taken into account. Additionally, our corresponding theoretical band-structure model predicts the existence of additional localized electronic acceptor and donor defect bands within the band gap of CuGaSe₂ originating from a strong covalent interaction between Ge4s and Se4p states for Ge atoms tetrahedrally surrounded by the Se nearest-neighbor atoms. A theoretically predicted antibonding Ge-Se4s p³ defect band appearing well above the Fermi level for the Ge _Ga¹⁺ point-defect system can be directly linked to a Ge-dopant-related donor-acceptor-pair transition as observed in our photoluminescence spectra.