Various one-dimensional nano-morphologies, such as multiporous nanofibers (MPNFs), porous nanofibers (PNFs), and nanowires (NWs) of SnO₂, are synthesized using electrospinning technique by controlling the tin precursor concentration. The MPNFs have ∼8-fold higher surface area compared to the other morphologies. Dye-sensitized solar cells (DSCs) were fabricated using these nanostructures as photoanodes and their performance was compared. The MPNFs surpass the performance of PNFs and NWs as well as conventional TiO₂ paste. Record photoconversion efficiency (PCE) of ∼7.4% was realized in MPNFs DSCs, which was twice to that achieved using PNFs (∼3.5%). Furthermore, the MPNFs showed over >80% incident photon to current conversion efficiency (22% higher than that achieved by spherical P25 TiO₂ particles) and also demonstrated ∼3 times longer electron lifetime and electron diffusion length. Owing to the possibility to produce large quantities using electrospinning technique, huge commercial potential of SnO₂ nanostructures, and promising results achieved herein, the MPNFs are expected soon to be utilized in commercial devices.