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 TiO 2 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. © 2010 The Royal Society of Chemistry.