Atomic layer deposited (ALD) Al2O3 films on Cu(In,Ga)Se2 (CIGS) surfaces have been demonstrated to exhibit excellent surface passivation properties, which is advantageous in reducing recombination losses at the rear metal contact of CIGS thin-film solar cells. Here, we report, for the first time, experimentally extracted electronic parameters, i.e. fixed charge density (Qf) and interface-trap charge density (Dit), for as-deposited (AD) and post-deposition annealed (PDA) ALD Al2O3 films on CIGS surfaces using capacitance–voltage (C-V) and conductance-frequency (G-f) measurements. These results indicate that the AD films exhibit positive fixed charges Qf (approximately 1012 cm−2), whereas the PDA films exhibit a very high density of negative fixed charges Qf (approximately 1013 cm−2). The extracted Dit values, which reflect the extent of chemical passivation, were found to be in a similar range of order (approximately 1012 cm−2 eV−1) for both AD and PDA samples. The high density of negative Qf in the bulk of the PDA Al2O3 film exerts a strong Coulomb repulsive force on the underlying CIGS minority carriers (ns), preventing them to recombine at the CIGS/Al2O3 interface. Using experimentally extracted Qf and Dit values, SCAPS simulation results showed that the surface concentration of minority carriers (ns) in the PDA films was approximately eight-orders of magnitude lower than in the AD films. The electrical characterization and estimations presented in this letter construct a comprehensive picture of the interfacial physics involved at the Al2O3/CIGS interface.