We describe a seeded hydrothermal process for the growth of unique double-sided brush-shaped (DSBS) TiO2 nanostructure assemblies consisting of highly ordered rutile nanowires vertically aligned around an annealed TiO2 nanoparticle layer. The annealed TiO2 nanoparticle layer seeds the nanowire growth and also supports the DSBS structure. The morphology of the DSBS TiO2 nanostructure depends on the hydrothermal reaction time. The diameter of the nanowires is about 6.6 nm, and with increasing reaction time from 1 to 8 h the nanowire length increases from 0.6 to 6.2 μm, whereas the thickness of the nanoparticle layer decreases from 4.3 to 2.8 μm. These free-standing nanowire arrays provide large internal surface area, which is essential for minimizing carrier recombination in high performance photovoltaic devices. Furthermore, the nanowire architecture can help increase the rate of charge transport as compared to particulate films because of lower concentration of grain boundaries. The power conversion efficiency of backside (DSBS TiO2/FTO photoanode) illuminated dye-sensitized solar cells fabricated using the DSBS TiO2 nanostructure assembly is found to be depended on the nanowire length. A cell fabricated using 15.2 μm thick nanostructures sensitized by N719 has a short-circuit current density of 12.18 mA cm(-2), 0.78 V open circuit potential, and a 0.59 filling factor, yielding a maximum power conversion efficiency of 5.61% under AM 1.5 illumination.