We have investigated the role of charge state of Ti in the electronic properties and structure of electrically conductive CMAS-TiO2-Pd glass and glass-ceramics by X-ray photoelectron spectroscopy, electron paramagnetic resonance, positron annihilation lifetime spectroscopy, and fluorescence spectroscopy. These studies suggest the concentration of Ti3+ ions was, at most, similar to 0.1wt% in glass-ceramics devitrified in the reducing atmosphere of forming gas; no other glass or glass-ceramic samples exhibited measurable levels of Ti3+. The observed fluorescence at liquid nitrogen temperature in parent glasses and glass-ceramics obtained in air is explained by UV-induced charge-transfer processes involving Ti4+ ions and oxygen surroundings. The X-ray photoelectron spectroscopy data are correlated with rutile, anorthite, diopside, and titanite crystalline phases identified in Pd-free and Pd-doped Ti:CMAS glass-ceramics earlier.