(Mg0.88, Fe0.12)SiO3, (Mg0.86, Fe0.14)(Si0.98, Al0.02)O3 perovskites were studied using Fe K-edge X-ray Absorption Near Edge Spectroscopy (XANES) under pressure up to 85 GPa at ambient temperature. The amount and quality of the data collected allows to perform for the first time a systematic study of the absorption edge features as a function of pressure in this geophysically important system and permits to qualitatively confirm the presence of electronic transition in (Mg, Fe)(Si, Al)O3 perovskite at 35–85 GPa, which according to Mössbauer data can be associated with the gradual high spin-intermidiate spin crossover.