Crack-free, micron-thick, worm-like mesoporous TiO2 films with an anatase phase, organized pores, and good interconnectivity were prepared by the self-assembly of anionically polymerized polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) block copolymer and hydrophilically preformed TiO2 nanocrystals. The polymer concentration and polymer:TiO2 ratio were carefully adjusted to systematically vary the TiO2 structure and evaluate the effects on the performances of solid-state dye-sensitized solar cells (ssDSSCs). As evaluated by scanning electron microscopy (SEM), grazing incidence small-angle X-ray scattering (GI-SAXS), and N-2 adsorption-desorption measurements, the use of a higher polymer concentration (6 wt%) and a polymer:TiO2 ratio of 1:2, referred to as P6T2, resulted in a worm-like structure with a large surface area and smaller mesopores, whereas an aggregated structure with bimodal pores was obtained with a polymer:TiO2 ratio of 1:1. An efficiency of 4.0% was obtained at 100 mW/cm(2) when using a 2.8 mu m thick P6T2 film as a photoanode in a ssDSSC, which is much greater than the efficiency of commercially available paste (2.3%) with a similar film thickness. The higher efficiency of the P6T2 cells is due to the improved current density, resulting from its larger surface area, well-organized pores, and good interconnectivity. (c) 2013 Elsevier Ltd. All rights reserved.