Core–hole spectroscopies such as x-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HR-EELS) in combination with multiplet calculation are important tools to elucidate the electronic structure of transition metal compounds. This work presents a comparison between the electronic structure obtained by XPS and HR-EELS for polycrystalline perovskite-type Ba_0.9Ca_0.1Ti_0.9Zr_0.1O₃. Raman analysis suggests that Ca²⁺ cations could partly occupy the Ti⁴⁺ cations in the B-site of a perovskite structure with the tetragonal phase. A multiplet structure was determined by XPS for Ti 2p and by HR-EELS for Ca L_2,3 and Ti L_2,3 edges. Octahedral (O_h) symmetry in the crystal field (CF) effects reproduces the local distortion of TiO₆ octahedra. The charge transfer (CT) effects were also considered to reproduce L₃-edge EELS shoulders and the satellite in the Ti 2p XPS region. CF and CT parameters, 10 D_q, (charge transfer energy) Δ, and (Coulomb repulsion energy) U_dd, are reported for future reference. The broadening of the Ti L₂-edge suggests the presence of the Coster–Kronig electron decay process. Multiplet calculation in O_h symmetry for the Ca L_2,3-edge could support the Raman interpretation.