In this study, we demonstrate the surfactant-assisted synthesis of uniform-sized titania microspheres and their clusters for highly responsive optical materials. Monodisperse titanium glycolate microspheres were produced by controlled hydrolysis of glycolated titanium butoxide in acetone using surfactant as a stabilizer. The diameter of as-prepared particles ranged from 230 to 650 nm and was finely controlled by changing the concentrations of titanium butoxide and surfactant. In particular, the tunable range of the particle size was at a few tens of nanometers scale by the surfactant concentration, which was much finer than that by the concentration of titanium butoxide. Then, as-prepared titanium glycolate microspheres were transformed into monodisperse titania microspheres of anatase phase by heat treatment. Pure clusters of titania microspheres with an identical configuration were obtained by encapsulating a certain number of microspheres in emulsion droplets and subsequently evaporating the emulsion phase to induce self-assembly. Dynamic and static light scattering experiments show that the pure clusters with an identical configuration were well dispersed, and the refractive index of anatase phase titania microspheres was about 2.2. In addition, monodisperse Eu-doped titanium glycolate microspheres were prepared for phosphorescence sources by adding both a soluble precursor Eu(NO3)(3)center dot 5H(2)O and glycolated titanium butoxide in acetone. Finally, photoluminescence properties of Eu-doped titania microspheres were examined after annealing.