We report a novel method to synthesize nanocomposites composed of titania nanoparticles and phosphotungstate ions with various composition ratios ranging from W/Ti = 12/10 to 12/500 by inducing the electrostatic interaction between the positively charged protonated titania sol-particles and the negatively charged phosphotungstate anions to flocculate and precipitate. The precipitates showed varied features depending on the composition. The precipitate from the tungsten-richest W/Ti = 12/10 reaction is amorphous in its powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy data. This material shows the Type II adsorption characteristics in its N2-adsorption isotherm, but with quite low surface area of 34 m2/g. To the contrary, the precipitates from the titanium-richer reactions (W/Ti = 12/50- 12/500) are composed of anatase nanoparticles of 2-6 nm by XRD, TEM and Raman and show the Type I adsorption characteristics. The surface area linearly increases with the titanium content from 131 m2/g for W/ Ti = 12/50 to 228 m2/g for 12/500. The precipitate from the reaction with the intermediate composition W/Ti = 12/20 is composed of anatase nanoparticles and does not have any pore accessible to N2. With the wide variety of the physical properties of the precipitates, the present method can be a novel, viable means to tailor synthesis of nanocomposite materials. A formation mechanism of the precipitates is based on the electrostatic interactions between the titania nanoparticles and phosphotungstate ions.