Herein, we explore the idea of self-assembly of nearly monodisperse nanoparticles as uniform building blocks to design highly crystalline mesoporous TiO(2) nanoparticles, through evaporation-induced self-assembly (EISA) and hydrothermal methods by using non-ionic Pluronic F127 and anionic surfactant SDS, respectively as structure directing agents. The small- and wide-angle powder X-ray diffraction and transmission electron microscopy (TEM) are used to characterize the mesophases. N(2) adsorption-desorption studies and high-resolution TEM results further reveal that mesopores are formed by the arrangement of the nanoparticles of size ca. 4.0-5.0 nm for SDS-templated and 8.0-9.0 nm for F127-templated TiO(2) nanoparticles with broad interparticle pore size distribution. Optical properties of these nanomaterials are studied by UV-visible diffuse-reflectance spectroscopy, photoluminescence (PL) and time-resolved fluorescence (TCSPC). These nanostructured titania exhibited excellent catalytic activity in the photodegradation of ecologically abundant dyes Methylene blue and Rose Bengal under UV-visible light irradiation.