One of the main advantages of photonic crystal fibers (PCFs) is their ability to host novel functional materials in the airholes of the cladding. Here, we demonstrate a unique post-processing method which allows the integration of materials with significantly different thermo-mechanical properties inside the voids of silica PCF. We first present the material properties of silica, As2Se3 and polydimethylsiloxane (PDMS) in terms of their refractive indices and viscosity profile. The latter suggests that the proposed materials are not suitable for direct fiber drawing and thus we present the development of a multi-material As2Se3/PDMS/Silica PCF based on a solution-processed and pressure-assisting method. The integration of both As2Se3 chalcogenide glass films and PDMS was made in ambient conditions using a costeffective approach. The deposition of the high-index chalcogenide glass films revealed distinct resonances in the visible and near-infrared region while the high thermo-optic coefficient of PDMS provides the ability to thermally control the intensity of the antiresonant bands. The proposed method opens new directions towards multimaterial silica-based PCFs for novel tunable devices and sensors.