Composites with enhanced refractive index have been synthesised through a sol–gel process. A refractive index of approximately 1.70 has been achieved at a concentration of 75 wt% TiO2. The refractive index increases with the concentration of TiO2. The influence of the concentration of TiO2 on the mechanical properties has been studied. The potential application of these materials in photonics area has been demonstrated by fabricating multi-layer spherical voids in them through a femtosecond laser-driven micro-explosion method.