AbstractTwo photon photopolymerization (2PP) is a new and modern method in solid freeform fabrication. 2PP allows the fabrication of sub-micron structures from a photopolymerizable resin. By the use of near-infrared (NIR) lasers it is possible to produce 3D structures with a spatial feature resolution as good as 200 nm. This technique can be used in polymer-based photonic and micro-electromechanical systems (MEMS), for 3D optical data storage or for the inscription of optical waveguides based on a local refractive index change upon laser exposure. Since the 2PP only takes place inside the focus of the laser beam, complex 3D-structures can be in-scri-bed into a suitable matrix material.In the presented work, 2PP is used to write optical waveguides into a prefabricated mechanically flexible polydimethylsiloxane matrix. The waveguides were structured by selectively irradiating a polymer network, which was swollen by a monomer mixture. The monomer was polymerized by two photon photopolymerization and the uncured monomer was removed by evaporation at elevated temperatures. This treatment led to a local change in refractive index in the order of Δn = 0.02, which was significantly above the industrial requirement of Δn = 0.003. The measured optical losses were around 2.3dB/cm. Since all unreacted monomers were removed by eva-po-ration, the final waveguide was stable up to temperatures of more than 200°C.In a second approach highly porous sol-gel materials (based on tetramethoxysilane (TMOS) as precursor and the surfactant cetylpyridinium chloride monohydrate as structural temp-late) were utilized as matrix materials. The precursor was organically modified with poly(ethylene glycol) spacers in order to increase the toughness and thus facilitate the fabrication of transparent porous monoliths and flexible films. The pores of the sol-gel-derived matrix were filled with acrylate-based monomers of high refractive index and after selective irradiation using 2PP waveguides (Δn = 0.015) could be written into the material.