Rugby-shaped anatase TiO2 hollow nanoparticles (TiO2-HNP), predominantly 100–150 nm in length (along long-axis) and 80–120 nm in diameter (along short-axis), were for the first time fabricated in a large quantity by the H2O2-assisted fluoride induced self-transformation strategy. H2O2 and fluoride ions not only play key roles in the formation of TiO2 hollow nanoparticles, but also enhance their crystallization. Importantly, the as-prepared TiO2-HNP show enhanced photocatalytic activity, ascribed to the synergistic effect of good crystallinity and the special hollow structure of TiO2-HNP.