The structure of electrically conductive CMAS-TiO2-Pd glass and ceramics was investigated by transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), and extended X-ray absorption fine structure spectroscopy (EXAFS). The XANES spectra of Ti do not show any significant difference between the glasses ceramized in air or in a reducing forming gas, as well as between Pd-containing versus Pd-free samples, nor between surface versus bulk of the glass-ceramic samples. However, EXAFS and XANES data recorded at the Pd K-edge show significant dependences on whether the glass-ceramic was ceramized in air or in forming gas. The XPS spectra of Ti 2p core-level electrons for glasses ceramized in air or forming gas also show a strong difference depending on whether the samples did or did not contain Pd. STEM mapping confirms the existence of grains in the form of main crystalline phases identified with XRD, and also reveals the existence of Pd nanoparticles in glasses ceramized in both air and in forming gas.