The H 2 plasma modification of polydimethylsiloxane (PDMS) films of initial thickness up to 600 nm was studied. The main plasma component modifying the films is the VUV plasma radiation measured by a VUV monochromator. By variation of the plasma processing parameters, such as H 2 pressure, RF forward power and treatment time, the optimum parameters are defined for the plasma chemical modification of liquid PDMS films. The thin films were analysed by Infrared Reflection Absorption Spectroscopy. Gradually changes in the vertical films structures is found with a top methyl-free SiO x layer ( 60 nm), followed by a crosslinked bulk material with a gradually increasing CH 3 concentration over the film depth. Additionally, the PDMS plasma modifications results in films shrinkages as measured by Spectroscopic Ellipsometry (SE).