Titania-polymer nanohybrid thin films represent a new class of potential materials for optoelectronic applications. While most such nanohybrid thin films lack control in crystallinity, we report in this paper transparent nanohybrids of titania-polymethyl methacrylate (TiO2-PMMA) thin films having a remarkably enhanced nanocrystallinity. Post-treatments with water vapor at relatively low temperatures were applied on these thin films, following in situ sol-gel polymerization. They promoted rearrangement of flexible Ti-O-Ti bonds leading to enhanced crystallization of the TiO2 phase. The degree of TiO2 crystallinity in the resulting nanohybrid films was studied by using XRD, FTIR, UV-Vis spectroscopies and HRTEM. Both linear and nonlinear optical responses increase with the enhancement of TiO2 crystallinity in the nanohybrids. The highest two-photon absorption coefficient (β) and nonlinear refractive index (n2) were observed for the nanohybrid thin films with highest TiO2 crystallinity, as confirmed by open and closed aperture Z-scan techniques using 250 fs laser pulses at 800 nm, having a value of 2260 cm GW-1 and 6.2 × 10-1 cm2 GW-1, respectively.