This article describes a cell architecture that achieves enhanced light harvesting with less dye quantity while simultaneously improving the performance of the polysiloxane-based solid-state dye-sensitized solar cells (DSSCs). We report the synthesis of bimodal mesoporous anatase TiO2 films by a dual templating approach, combining a block-copolymer template (Pluronic P123) and polystyrene nanospheres (PS) as soft and hard templates, respectively. The AFM and TEM analysis of TiO2 films revealed a mixture of mesoporous and macroporous morphology in which dual porosity is generated by combustion of soft and hard templates. The size of the macropores was varied by employing PS beads with different diameters (62, 130 and 250 nm). The influence of the macropore size on the dye loading and pore infiltration is the main purpose of this article. The bimodal porosity leads to increased light scattering due to enhanced optical path length, and better pore infiltration of the polysiloxane electrolyte is achieved. The amount of dye uptake by the dual films is lower than that of soft films because the large pore size reduces the total surface area. The optimum bimodal structure was obtained when combining P123 surfactant and the 130 nm PS beads leading to the lowest charge transfer resistance and a high efficiency for DSSCs is reported with both liquid and polymer electrolytes. Even if the dye uptake was lower, the photovoltaic performance has been maintained and improved in some devices. The open circuit voltage and fill factor were improved, owing to a successful joining of different effects i.e. increased light harvesting, facile electrolyte penetration and reduced charge recombination.