Specific features of the charge-transfer states and O2p → V3d transitions in the (VO6)9− octahedral complex are studied using the cluster approach. The reduced matrix elements of the electric-dipole transition operator are calculated for many-electron wave functions corresponding to the initial and final states of a charge-transfer transition. Using a parameterization of the results, the relative intensities of the allowed charge-transfer transitions are calculated disregarding the mixing of different configurations of the same symmetry. The Tanabe-Sugano theory is used with inclusion of this mixing to calculate the energies of many-electron charge-transfer transitions and their actual intensities. Modeling of the optical spectrum of LaVO3 reveals a complicated charge-transfer transition band consisting of 81 lines. The main maxima of the band are in the range 6.3–7.3 eV. There are also additional maxima in the regions of ≈3 and ≈8–9 eV. The bandwidth is ≈10 eV. The results of model calculations are in agreement with experiments and demonstrate the weakness of the widely used assumption that the spectrum of charge-transfer transitions has a simple structure.