A new organic–inorganic hybrid material (HYBRIMER) has been synthesized homogeneously through a non-hydrolytic sol–gel process. The new HYBRIMER shows efficient index control and minor volume contraction behavior during micro-scale molding. In hybrid materials, the methacrylic end-group is considered suitable for cross-linking during the UV curing step, while the fluorinated functionality is appropriate for refractive index control. As the fluorinated silane contents are varied, the structural evolution and refractive index of the synthesized resin are then controlled (1.469 to 1.513 at 850 nm). A large core optical waveguide structure is formed by these hybrid materials, which exhibit low near IR wavelength absorption. A single material system is applied to both the core and the cladding materials of the optical waveguide. The measured optical propagation loss is lower than 0.25 dB cm−1.