Macroporous TiO 2 photoanodes for Dye-sensitized Solar Cells (DSCs) were synthesized by new one-pot method combining sol–gel chemistry, emulsion templating and doctor-blade 2D deposition technique. Multi-step deposition followed by annealing at 500 °C yielded up to 30-μm thick anatase TiO 2 films exhibiting a complex porous structure including micro-, meso- and macropores. After sensitization with a commercial ruthenium dye, the photovoltaic performance of the films in DSCs was related to their structural properties, and their efficiency was compared to those of P25 reference photoanodes. The easily-processed macroporous photoanodes showed encouraging performance, almost reaching 4%, with enhanced light scattering at high wavelengths and improved light-harvesting properties.