We present a material and device based study on the fabrication of mesoporous TiO2 and its integration into dye-sensitized solar cells. Poly(isoprene-block-ethyleneoxide) (PI-b-PEO) copolymers were used as structure directing agents for the sol–gel based synthesis of nanoporous monolithic TiO2 which was subsequently ground down to small particles and processed into a paste. The TiO2 synthesis and the formation of tens of micrometre thick films from the paste is a scalable approach for the manufacture of dye sensitised solar cells (DSCs). In this study, we followed the self-assembly of the material through the various processing stages of DSC manufacture. Since this approach enables high annealing temperatures while maintaining porosity, excellent crystallinity was achieved. Internal TiO2 structures ranging from the nanometre to micrometre scale combine a high internal surface area with the strong scattering of light, which results in high light absorption and an excellent full-sun power conversion efficiency of up to 6.4% in a robust, 3 μm thick dye-sensitized solar cell.