AbstractThis study aims at identifying compounds incorporated into Polydimethylsiloxane (PDMS) which produce large refractive index change under fs laser exposition, potentially leading to optimal writing of waveguides or photonic devices in such a soft host. Germanium derivative, titania and zirconite derivatives, benzophenone (Bp), irgacure-184/500/1173 and 2959 are investigated. We show a mapping of the RI index change relative to the writing speed (1 to 40 mm/s), the repetition rate (606 to 101 kHz) and the number of passes (1 to 8) from which we establish quantitative parameters to allow the comparison between samples. We show that the organic materials, especially irgacure-184 and benzophenone yield a significantly higher maximum refractive index change in the order of 10−2. We also show that the strongest photosensitivity is achieved with a mixture of organic/organo-metallic material of Bp + Ge. We report a synergetic effect on photosensitivity of this novel mixture.