Flexible dye-sensitized solar cells (DSSCs) often face the dilemma of the high temperature sintering of TiO2 photoanode to achieve superior performance and low thermal durability of the flexible substrate. Herein, we report a photoanode that combines the flexibility and high-temperature durability, which circumvents the long-standing challenge in flexible photoanode of DSSC. A hybrid mat consisting of anatase-phased TiO2 nanofibers and structurally amorphous SiO2 nanofibers is first prepared via the method of dual-spinneret electrospinning followed by pyrolysis. The hybrid fibrous mat is then impregnated with binder-free TiO2 nanoparticles and sintered at 480 degrees C to form a flexible composite photoanode for DSSC. The DSSC based on this composite photoanode achieves a power conversion efficiency of 6.74 +/- 0.33% on FTO/glass substrate. Device characterization and phototransient measurement, dye-loading experiment, and structural characterization composite photoanode, the TiO2 nanopartides enhance the dye loading, the TiO2 nanofibers improve the electron transport, and the SiO2 nanofibers provide the mechanical strength/flexibility. The freestanding composite mat of TiO2 nanopartides and electrospun TiO2/SiO2 nanofibers, as well as the preparation methods reported herein, not only is ideal for flexible DSSCs, but also can be applied for a broad range of flexible and low-cost energy conversion devices.