Due to its biocompatibility poly(dimethylsiloxane) (PDMS) is an important material for the development of microelectromechanical systems or long-term, medical implants. The paper describes the morphology modifications and surface chemistry of PDMS during pulse laser treatment. SEM, μ-Raman spectroscopy, X-ray micro-tomography and XPS analyses are applied. PDMS decomposition takes place as a function of laser energy absorption. This leads to different oxidation degree of silicon, as shown by the curve fitting of Si 2p and O 1s. The irradiated parts become hydrophilic in contrast with the rest of the material, which remains hydrophobic. This is the condition enabling successful selective electroless deposition of Ni in the tracks, excluding the usual preceding sensibilization and chemical activation. This process is accomplished successfully after femtosecond laser irradiation and it is found that the time interval between laser treatment and metallization is not a critical parameter.