A series of uniform and well-dispersed TiO2 spheres have been successfully synthesized through a controlled hydrolysis route by using different titanium alkoxides as reactants. The types of titanium alkoxides and stirring time have an effect on the uniformity and dispersion of the TiO2 spherical particles. The addition of a small amount of salt also plays a crucial role for the formation of the monodisperse TiO2 spheres. Under ultraviolet excitation, the as-obtained Eu(3+)-doped TiO2 spheres exhibit red emission corresponding to the electric-dipole allowed 5D0-7F2 transition of Eu3+ ions, which is induced by the lack of inversion symmetry at the Eu3+ ions site. The Eu(3+)-doped TiO2 phosphors might find potential applications in the fields such as optical displays, photoelectric devices, and light-emitting diodes (LEDs).