Titanium dioxide/poly(methyl methacrylate) (TiO2/PMMA) hybrid films with various amounts of TiO2 containing PMMA resin on PMMA sheets were produced by a tape casting method. TiO2 nanocrystals were prepared using electrospraying process at 400oC under high electric field of 3 kV/cm. The as-sprayed and annealed TiO2 powders were characterized by Raman spectroscopy, XRD, SEM and TEM. The UV absorption for both pristine PMMA sheet and TiO2/PMMA hybrid film on PMMA sheet was measured using UV-Vis spectroscopy. The as-sprayed and annealed TiO2 powders showed anatase preferred orientation. They have higher UV absorption in the range of wavelength between 230 and 370 nm than commercial anatase TiO2 nanopowders. Moreover, the visible light transmittances of anatase TiO2/PMMA hybrid films on PMMA sheets in the range of wavelength between 400 and 800 nm was comparable with those derived from pristine PMMA sheets. Therefore, the resulting hybrid films can block out the UV rays, but are transparent to visible light.