A facile process to fabricate highly crystalline mesoporous N,B codoped TiO₂ is introduced. The N,B codoped TiO₂ nanomaterial, which has controlled crystallographic phase, size and unique nanoshape, is successfully applied to an enhanced device for dye-sensitized solar cells (DSCs) with an open-circuit photovoltage of 0.823 V and yielding a high overall energy conversion of 8.4%. A DSC based on the N,B codoped TiO₂ electrode shows a competitive photovoltaic performance compared with the undoped DSC, which is attributed to the ideal combination of superior energy band structure and retarded electron recombination from the unique N,B codoped TiO₂ particle structure.