Crystalline niobium-doped titania nanoparticles were synthesized via solvothermal procedures using tert-butyl alcohol as a novel reaction medium, and their assembly into mesoporous films was investigated. The solvothermal procedure enables the preparation of crystalline doped and undoped nonagglomerated titania nanoparticles, whose size can be controlled from 4 to 15 nm by changing the reaction temperature and time. The anatase lattice of these particles can incorporate more than 20 mol % of Nb ions. The nanoparticles can be easily dispersed at high concentrations in THF to form stable colloidal suspensions and can be assembled into uniform porous mesostructures directed by the commercial Pluronic block copolymer F127. The resulting mesoporous films show a regular mesostructure with a d spacing of about 17 nm, a uniform pore size of about 10 nm with crystalline walls, a high porosity of 43%, and a large surface area of 190 m(2) cm(-3). Substitutional doping with niobium ions drastically increases the electrical conductivity of the titania particles. The electrical conductivity of as-prepared nanoparticles containing 20 mol % of Nb is 2 x 10(-5) S cm(-1); it increases to 0.25 S cm(-1) after treatment at 600 °C in nitrogen.