Abstract The studies of niobium after electrochemical polishing EP in sulfuric–methanesulfonic acid mixture were performed. The NbO x /Nb surface was studied by SEM/EDX and XPS methods to find out the chemical composition of the oxygen-induced structures. Specifically the XPS results obtained after EP treatment indicate prevailing part of oxygen with niobium oxides on the sample surface. In order to correctly interpret these structures the photoelectron spectra of main niobium oxides were analyzed, and the spectra of internal Nb 3d and O 1s electronic states and valence band spectra were measured for them.