Scanning tunneling microscopy (STM) methods are used to characterize hydrogen‐terminated Si surfaces prepared by a novel method. The surface preparation method is used to expose the Si–SiO2 interface. STM images directly reveal the topographic structure of the Si–SiO2 interface. The dependence of interface topography on oxide preparation conditions observed by STM is compared to the results of conventional surface characterization methods. Also, the electronic structure of the hydrogen‐terminated surface is studied by STM spectroscopy. The near‐ideal electronic structure of this surface enables direct tunnel spectroscopy measurements of Schottky barrier phenomena. In addition, this method enables probing of semiconductor subsurface properties by STM.