Grain boundaries (GBs) in polycrystalline Cu(In,Ga)Se2 thin films exhibit only slightly enhanced recombination, as compared with the grain interiors, allowing for very high power-conversion efficiencies of more than 20% in the corresponding solar-cell devices. This work highlights the specific compositional and electrical properties of Cu(In,Ga)Se2 GBs by application of appropriate subnanometer characterisation techniques: inline electron holography, electron energy-loss spectroscopy, and atom-probe tomography. It is found that changes of composition at the GBs are confined to regions of only about 1 nm in width. Therefore, these compositional changes are not due to secondary phases but atomic or ionic redistribution within the atomic planes close to the GBs. For different GBs in the Cu(In,Ga)Se2 thin film investigated, different atomic or ionic redistributions are also found. This chemical flexibility makes polycrystalline Cu(In,Ga)Se2 thin films particularly suitable for photovoltaic applications.