We report a unique one-dimensional (1-D) morphology of TiO2 having TiO2 nanoparticles decorating the surface of TiO2 nanofibers fabricated by simultaneous electrospinning and electrospraying technique. The composite made by both nanofibers and nanoparticles is used as a photoanode material for dye-sensitized solar cells (DSCs) which helped in overcoming the limitations associated with nanofibers and nanoparticles when employed separately. The DSC showed an excellent efficiency of 7.89% (for a square-shaped cell of area 0.2 cm2) in comparison to 6.87 % for the nanoparticulate DSC and 5.21% for the nanofiber DSC (for cells of same area and thickness) which is an impressive value when literature on DSC fabrication with 1-D nanostructures for DSCs is concerned.