ABSTRACTPolycrystalline widegap Cu(In,Ga)Se2 (CIGSe) absorbers for top cells in photovoltaic tandem devices can be synthesized via [Ga]/([Ga] + [In]) (GGI) ratios of > 0.5. However, the power conversion efficiencies of such high‐GGI devices are smaller than those of the record cells with GGI < 0.5. In the present work, the effects of the GGI ratio on various CIGSe material properties were studied and correlated with the radiative and nonradiative open‐circuit voltage (VOC) deficits of the thin‐film solar cells. Average grain sizes, grain boundary (GB) recombination velocities, fluctuations in luminescence energy distribution, barrier heights at GBs, effective electron lifetimes, and Urbach energies were investigated in five solar cells with GGI ratios from 0.13 to 0.83. It was found that the GGI variation affects GB recombination velocities, fluctuations in spatial luminescence distributions, the average grain size, the electron lifetime, and the Urbach energy. In contrast, the detected ranges of barrier heights at GBs are independent of the GGI ratio. Mainly Ga/In gradients give rise to substantial radiative VOC losses in all solar cells. Nonradiative VOC deficits are dominant especially for solar cells with GGI > 0.5, which can be attributed to low bulk lifetimes and enhanced recombination at GBs in CIGSe absorbers in this compositional range.