In this paper we study by high resolution scanning transmission electron microscopy coupled with electron energy-loss spectroscopy (STEM-EELS) an oxide dispersion-strengthened (ODS) steel with the nominal composition Fe–14Cr–1W–0.3TiH2–0.3Y2O3 (wt.%) designed to withstand the extreme conditions met in Gen. IV nuclear reactors. After denoising via principal component analysis (PCA) the data are analyzed using independent component analysis (ICA) which is useful in the investigation of the physical properties and chemical structure of the material by separating the individual spectral responses. The Y–Ti–O nanoparticles are found to be homogeneously distributed in the ferritic matrix, sized from 1 to 20nm and match a non-stoichiometric pyrochlore-Y2Ti2O7−δ structure for sizes greater than 5nm. We show that they adopt a (Y–Ti–O)–Cr core–shell structure and that Cr also segregates at the matrix grain boundaries, which may slightly modify the corrosion properties of the steel. Using Ti-L2,3 and O-K fine structure (ELNES) the Ti oxidation state is shown to vary from the center of the nanoparticles to their periphery, from Ti4+ in distorted Oh symmetry to a valency often lower than 3+. The sensitivity of the Ti “white lines” ELNES to local symmetry distortions is also shown to be useful when investigating the strain induced in the nanoparticles by the surrounding matrix. The Cr-shell and the variation of the Ti valence state highlight a complex nanoparticle–matrix interface.