Different polymeric materials were investigated for their suitability as novel inert matrix materials, used for two-photon patterning of three dimensional optical waveguides. By investigating different PDMS based materials containing photo-polymerisable monomers, waveguides were able to be inscribed into the material using two-photon photopolymerisation. To produce the optical waveguides, an ultra fast femto second laser was used to induce a photopolymerisation of functional monomers, either added to the polymeric material, or directly attached to the polymer backbone. This enabled the production of true three dimensional waveguide structures to be embedded into the material in a single step. Cross-linked materials based on a hydride terminated polysiloxane containing high refractive index methacrylate monomers, an epoxy propoxy terminated polysiloxane cross-linked with a diamine, containing acrylate monomers, and a silanol terminated polysiloxane, containing acrylate functional groups attached to the polymer backbone were fully characterised and investigated for their suitability as optical materials used for waveguide applications. Each matrix material was characterised by FT-IR, STA and near-infrared spectroscopy as well as ellipsometry to determine the refractive index difference between the waveguide core and cladding material. Optical and phase contrast microscopy were used to observe the waveguide core, with cut back measurements and RNF measurements carried out on the more successful waveguides. Successful matrix materials were used in the development of demonstrators, by accurately inscribing optical waveguides between laser and photo diodes on specially designed printed circuit boards. The demonstrators were then used to monitor the long term stability of the polymeric material as well as the optical waveguides, by detecting the photocurrents.