The initial stages of porous Si formation on Si(I 11) in dilute ammonium fluoride solution are analysed by photoelectron spectroscopy using synchrotron radiation (SRPES). The PES results in the por-Si formation regime partly support a recent dissolution model. The contribution from the Si 2p surface core level shift shows that 0.35 ML of the surface is still H-terminated after interruption of the conditioning process at the first photocurrent maximum. Two signals shifted in binding energy by 0.8 and I eV, respectively, are attributed to reaction intermediates expected from the proposed reaction mechanism and from theoretical calculations using density functional theory (DFT). A distinct roughening is found in in-situ AFM measurements, with a calculated RMS roughness parameter of 2.6 nm.