Topographical and electronic and properties of step bunched Si(111), prepared by electrochemical processing in alkaline solution, are analyzed. Tapping mode atomic force microscopy (TM AFM) analysis shows that one bunched step consists of about 15 atomic steps (each 0.314 nm in height) and that the (111) oriented terraces have widths that range from 150 to 250 nm. Scanning tunneling microscopy (STM) experiments show a corrugation of the (111) terraces with an rms roughness of 0.5–0.8 nm, correlated with etch pits in alkaline solution. Low energy electron diffraction (LEED) data show a splitting of the (10) and (01) spot from which a minimum terrace width of 4.8 nm have been calculated in good agreement with the TM AFM data. Kelvin probe force microscopy (KPFM) experiments show a decrease of the contact potential difference (CPD) at and near the edges of steps indicating a more negatively charged surface area. Synchrotron radiation photoelectron spectroscopy (SRPES) on electrochemically and purely chemically prepared step bunched surfaces is compared. From the Si 2p core level shift, and, in particular, from the onset of the valence band emission, an accumulation layer-type shift is observed on the electrochemically prepared sample that is absent for chemical preparation. The move of the Fermi level toward the conduction band minimum of the electrochemically conditioned samples is interpreted by H incorporation and discussed by a doping model that involves the mechanism of hydrogen evolution.