The surface condition of electrochemically H-terminated Si is compared with the situation at the first photocurrent maximum in dilute acidic ammonium fluoride solution where the divalent dissolution converts into the four-valence process. The first high spectral-resolution photoelectron spectroscopy data using synchrotron radiation of electrochemically hydrogenated Si are presented. A combined electrochemistry/ultrahigh vacuum surface analysis system, attached to the U 49/2 beamline at the synchrotron Bessy II, is used for photoelectron spectroscopy (PES) of the electrochemically conditioned samples. We analyze the Si 2p, O 1s, and F 1s core levels. A comparison of a density functional theory calculation of the reaction sequence, proposed in the dissolution model of Gerischer and co-workers, with the PES results supports this model. The anodized sample is characterized by a residual H coverage of 0.35 monolayers evidenced by a surface core level shift, Si-OH and Si-F-x species, F-, and a higher oxidized Si species. SiO2 is not found. Even on very well H-terminated surfaces, we find residual Si-OH complexes, fluoride and water. In situ atomic force microscopy shows a roughening with a root mean square roughness parameter of 2.6 nm. (C) 2003 The Electrochemical Society.