Nanosized Zr-doped TiO2 with improved structural stability and photocatalytic properties was synthesized by the sol-gel method. The physicochemical and morphological properties of the catalyst were investigated by transmission electron microscopy, thermogravimetric analysis, differential thermal analysis, X-ray diffraction, and Brunauer-Emmett-Teller analysis. Zr-doped TiO2 possessed a mesoporous structure and a noticeably increased surface area (90 m2 g−1) as compared with pristine TiO2 (28 m2 g−1). On doping with Zr, TiO2 exhibited reinforced texture, improved thermal stability, and enhanced photocatalytic properties. The electrochemical and photoelectrochemical characteristics of the samples were examined by Mott-Schottky analysis and sweep voltammetry under both dark and light conditions.