Our recent studies of oxidation processes on high-index silicon surfaces are reviewed. Interface trap densities, D it , at the thermally oxidized Si surfaces were systematically investigated for (001), (111), (110), (120), (331) and (113) orientations. Structure model of the SiO 2 /Si interface on (113) substrate was proposed based on the analysis of the optical measurements. The initial oxidation processes on high-index silicon surfaces with (113), (120) and (331) orientations at high temperatures have been investigated by Xray photoelectron spectroscopy, and the results were compared with the case of (001) orientation. It has been shown that monolayer oxidation on high-index silicon surfaces can be characterized through chemical shift in the core level of the Si 2p and O 1s states, and in addition through evaluation of oxide thickness, oxide composition and band bending.