Fe-deposited titanate nanotubes (Fe-TNTs) with high photocatalytic activity and adsorptive performance were synthesized through a one-step hydrothermal method. Initial As(III) oxidation followed by As(V) adsorption by Fe-TNTs could simultaneously remove these two toxic pollutants from aqueous solutions. The apparent rate constant value for photo-oxidation of As(III) under UV irradiation by Fe-TNTs was almost 250 times that of unmoidified TNTs. Under visible light, the Fe-TNTs also exhibited enhanced photocatalytic activity after Fe was deposited. Fe3+ located in the interlayers of TNTs acted as temporary electron- or hole-trapping sites, and attached α-Fe2O3 played the role of a charge carrier for electrons transferred from TNTs. These two effects inhibited electron–hole pair recombination thus promoting photocatalysis. Moreover, the As(V) adsorptive performance of Fe-TNTs also improved, owing to the presence of additional adsorption sites, α-Fe2O3, as well as increased pHPZC. Furthermore, Fe-TNTs exhibited good photocatalytic and adsorptive performace even after 5 reuse cycles. The present tests, concerning an initial As(III) photocatalysis and subsequent As(V) adsorption process, highlight the feasibility and importance of Fe used to modify TNTs. This study proposes a feasible method to simultaneously remove As(III) and As(V) from contaminated water using a novel Ti-based nanomaterial.