Na3[Ti2P2O10F], a novel oxyfluorinated titanium phosphate, is a promising anode material for lithium/sodium storage because of its open framework structure and marvelous two-dimensional (2D) tunnel. However, 2D nanostructured Na3[Ti2P2O10F] has been rarely prepared in view of the limitations of synthetic approaches. Here we report a one-step, low-cost solvothermal method for the synthesis of 2D ultrathin Na3[Ti2P2O10F] nanosheets with the thickness of 1∼2nm. Benefiting from the desired crystal and structural characteristics, these as-prepared ultrathin 2D Na3[Ti2P2O10F] nanosheets exhibit good electrochemical performance for Li-ion and Na-ion batteries.