A combination of solid-state voltammetry and Fourier transform infrared spectroscopy in the attenuated total reflectance mode was applied to identify earth pigments in samples from the frescoes of Antonio Palomino (dated 1707) taken from the vault of the Santos Juanes church in Valencia (Spain). Such frescoes suffered considerable damage by fire during the Spanish Civil War in 1936, resulting in severe chemical and chromatic alterations.