A systematic study on the desorption and dissociation kinetics of ethylene glycol and poly(ethylene glycol) oligomers (PEG) with masses ranging from 62 to 35 000 Da from a silica surface was undertaken. The measurements include characterization of the PEG-silica adsorption system using temperature programmed desorption, investigation of the surface coverage, and chemical composition during slow surface heating by real time x-ray photoelectron spectroscopy, and determination of translational energy distributions following nanosecond CO2 laser desorption. We found that even for heating rates exceeding 10(9) K/s desorption can be described by a thermal model. Intact desorption was limited to PEGs with masses less than or equal to 1000 Da for classical as well as for laser heating.