Dye sensitized solar cells (DSSC) photoanodes based on nanostructured materials have attracted much attention over the last decade due to their low cost and ease of manufacturing. A DSSC includes i) a photoanode composed of a glass plate on which is deposited a transparent conductive oxide (TCO) in contact with a semiconductor layer covered with a photosensitizing dye; ii) a counter-electrode made of platinum sputtered onto on a glass plate; and iii) an electrolyte placed between the two photoelectrodes. The photoanode should provide a large surface area to be in contact with the dye in order to transfer effectively the photogenerated electrons to the external circuit and TiO2 is the mostly used semiconductor material. The conventional manufacturing process of DSSC TiO2 layer requires a high temperature sintering step (~500°C) leading to a rigid/brittle structure. To solve this problem, an alternative method (electrospinning technique) is proposed in this work to develop at low temperature flexible PET/TiO2 porous structures with high surface area for DSSC photoanodes. Controlling the morphology/structure of TiO2 nanoparticles and PET/TiO2 nanocomposites is of key importance for developing high performance photoanode. Various shapes of TiO2 nanoparticles were synthetized by solvothermal method and characterized by TEM, XRD, UV-vis, and photoluminescence techniques in order to select the shapes with the best properties. Surface modification of TiO2 with cadmium sulfide (CdS) was also performed to extend their light absorption to the visible range. By a simple electrospinning process, we developed high surface area porous nanostructured PET/TiO2 and PET/TiO2-CdS mats without beads. Varying the electrospinning conditions allowed the production of mats with fibers diameter of 500 to 100 nm. Compared to nanocomposites fibers prepared with a commercial TiO2 P25, our resulting nanostructures show promising results with a better dispersion and smoother nanofiber surface.