Micro/nano-composite TiO2 porous films are prepared in a nutshell by the electro-hydrodynamic (EHD) method,and are applied to dye sensitized solar cells (DSSCs) successfully. Consideringthat micro/nano-composite structures based on the EHD technique are betterfor the filling of ionic liquid and quasi-solid-state electrolytes than liquid stateelectrolytes, a fill factor (ff) of 78.9% and a total photoelectric conversion efficiency(η) of 6.4% for ionic liquid electrolyte and an ff of 75.3% and anη of 5.3% for quasi-solid-state electrolyte are obtained. Moreover, this kind of compositehierarchical structure may be of benefit for light collection because of strong lightscattering. In order to obtain optimized devices, we probe into the influence of adding anamount of polymer on the photovoltaic performance, and find that by changing theconcentration of the polymer during the EHD process the specific surface area ofthe films changes, which leads to different photovoltaic behaviour of solar cells.