High refractive index materials are attractive for many photonic elements. For example, 3D photonic bandgap (PBG) materials have been proposed as the basis of many devices. In order to create complete 3D PBGs, materials enabling high refractive index contrast are needed. We here report on novel high refractive index hybrid polymers. They were synthesized by hydrolysis/polycondensation reactions of organo-alkoxysilanes and Ti alkoxide precursors, resulting in organically modified inorganic-oxidic pre-polymer resins. These can be organically cross-linked by one- or two-photon polymerization (2PP). The latter method enables the writing of arbitrary 3D structures. The introduction of Ti into the inorganic-oxidic network accounts for an increase in the material's refractive index, which could be varied between 1.62 and 1.8. Optical properties such as refractive index and absorption losses were determined on an exemplary material system in the lower refractive index range. The influence of the processing parameters on the degree of organic polymerization, and the refractive index of these novel high index materials was investigated in particular. 3D photonic crystal structures were written for the first time in a high-refractive index hybrid polymer.