Dye-sensitized solar cells (DSSC) with efficiencies greater than 4% were produced with templated "inverse opal" titania coatings. A novel one-step method produces uniform and crack-free coatings made using commercially available titania nanoparticles with high reproducibility and uniformity. In this research, a volatile solvent electrolyte was tested; however, it shows proof-of-concept that larger pore volumes can be created for increased penetration of more viscous electrolytes that can be utilized in high-efficiency cells. This dual size-scale porosity film is a promising structure for DSSC applications, especially for those solid-state or quasi-solid-state cells that require polymer electrolytes.