A lot of research on nanomaterials has been carried out in recent years. However, there is still a lack of nanostructures that have a combination of superior properties; both efficient electron transport and high surface area. Here, the authors have tried to develop hybrid α-Fe2O3 flower-like morphology which exhibits both superior electron transport and high surface area. Intrigued by the unique properties of Fe2O3 at the nanoscale and its abundance in nature, we have demonstrated a facile template-free solution based synthesis of hybrid α-Fe2O3 comprising nanopetals nucleating radially from a 3D core. Due to its simplicity, the synthesis process can be easily reproduced and scaled up. We carried out in-depth studies on gas sensing and dye-sensitized solar cell (DSSC) device characterization so as to gain an understanding of how surface area and transport properties are affected by variation in morphology. The hybrid α-Fe2O3 nanostructures are studied as potential candidates for gas sensors and for the first time as a working electrode for DSSC.