A new type of time-resolved photoelectron spectroscopy experiment is presented: the ESCA shifts of the 4d fine structure split core-level of iodine atoms in the iodophenylphenol molecules adsorbed perpendicular to the (100) surface of silicon has been studied and observed transiently in fs-time resolved photoelectron spectroscopy as a function of the delay between the exciting ultrashort UV pulse and the ionizing ultrashort XUV pulse.