Tailoring the nano-morphology and nano-architecture of titanium dioxide (TiO₂) is the most important task in the third generation solar cells (Dye sensitized solar cells/Quantum dot sensitized solar cells) (DSSCs/QDSSCs). In this article we present complete study of surfactant free synthesis of TiO₂ nanostructures by a simple and promising hydrothermal route. The plethora of nanostructures like nanoparticles clusters, 1D tetragonal nanorods, 3D dendrites containing nanorods having <30 nm diameter and 3D hollow urchin like have been synthesized. These nanostructures possess effective large surface area and thus useful in DSSCs. In the present work, 7.16% power conversion efficiency has been demonstrated for 3D dendritic hollow urchin like morphology. Our synthetic strategy provides an effective solution for surfactant free synthesis of efficient TiO₂ nanoarchitectures.