Two-dimensional (2D) anatase titanium dioxide (TiO₂) is expected to exhibit different properties as compared to anatase nanocrystallites, due to its highly reactive exposed facets. However, access to 2D anatase TiO₂ is limited by the non-layered nature of the bulk crystal, which does not allow use of top-down chemical exfoliation. Large efforts have been dedicated to the growth of 2D anatase TiO₂ with high reactive facets by bottom-up approaches, which relies on the use of harmful chemical reagents. Here, we demonstrate a novel fluorine-free strategy based on topochemical conversion of 2D 1T-TiS₂ for the production of single crystalline 2D anatase TiO₂, exposing the {001} facet on the top and bottom and {100} at the sides of the nanosheet. The exposure of these faces, with no additional defects or doping, gives rise to a significant activity enhancement in the hydrogen evolution reaction, as compared to commercially available Degussa P25 TiO₂ nanoparticles. Because of the strong potential of TiO₂ in many energy-based applications, our topochemical approach offers a low cost, green and mass scalable route for production of highly crystalline anatase TiO₂ with well controlled and highly reactive exposed facets.