A comprehensive multinuclear solid-state NMR study of scandium-substituted BaZrO3 is reported. Static low field and MQMAS very high field 45Sc NMR data revealed the presence of both 5- and 6-coordinated scandium atoms, 5-coordinated scandium arising from Sc nearby an oxygen vacancy. 17O NMR spectra showed the presence of up to three different chemical oxygen environments assigned to Zr–O–Zr, Zr–O–Sc and Sc–O–Sc. From the ratios of these different oxygen sites, the distribution of the scandium cations was close to random but indicated that the maximum scandium incorporation was lower than expected, consistent with the observation of Sc2O3 impurities at substitution levels of 30% Sc for Zr. 1H and 45Sc NMR data on the hydrated materials revealed the presence of scandium next to protonic defects. Finally, variable temperature 1H NMR showed the presence of at least two different proton environments in between which proton transfer occurs at ambient temperatures (300 K).