The advanced direct laser printing of functional devices with tunable effective index is a key research topic in numerous emerging fields, especially in micro-/nano-optics, nanophotonics, and electronics. Photosensitized nanocomposites, consisting of high-index materials (e.g., titanium dioxide, TiO2) embedded in polymer matrix, are emerging as attractive platforms for advanced additive manufacturing. Unfortunately, in the currently applied techniques, the preparation of optically functionalized structures based on these photosensitized nanocomposites is still hampered by many issues like hydrolysis reaction, high-temperature calcinations, and, especially, the complexity of experimental procedures. In this study, we demonstrate a feasible strategy for fabricating micro-/nanostructures with a flexibly manipulated effective refractive index by incorporating TiO2 nanoparticles in the matrix of acrylate resin, i.e., TiO2-based photosensitized nanocomposites. It was found that the effective refractive index of nanocomposite can be easily tuned by altering the concentration of titanium dioxide nanoparticles in the monomer matrix. For TiO2 nanoparticle concentrations up to 30 wt%, the refractive index can be increased over 11.3% (i.e., altering from 1.50 of pure monomer to 1.67 at 532 nm). Based on such a photosensitized nanocomposite, the grating structures defined by femtosecond laser nanoprinting can offer vivid colors, ranging from crimson to magenta, as observed in the dark-field images. The minimum printing width and printing resolution are estimated at around 70 nm and 225 nm, indicating that the proposed strategy may pave the way for the production of versatile, scalable, and functionalized opto-devices with controllable refractive indices.