In this work, synthesis and characterization of phenolphthalein-immobilized titania (T-phph) and silicatitania (ST-phph) nanomatrix is reported. The thin films are deposited by sol-gel method at low temperature. The effect of host-guest chemistry in matrices, on the surface structures, optical and sensing activity of the resultant thin films is studied. The phenolphthalein-immobilized fabricated nanoparticles/nanomatrices are analyzed by field emission scanning electron microscope, energy-dispersive X-ray spectroscopy, atomic-force microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, surface analysis, thermogravimetric analysis, and UV-Vis spectroscopy. Thermally stable and high surface area homogeneous nanoparticles, containing nanocrystalline anatase phase with low refractive index (1.58), low roughness (5.5 nm), and high transparency (95 %) are obtained for phenolphthalein-immobilized ST-phph nanomatrix. Moreover, smaller nanoparticles (56-121 nm) with good incorporation of dye and good response of sensing are obtained. The sensor response is optimized at pH 12 with 10.