Abstract Hydrogenated titanium dioxide has attracted intensive research interests in pollutant removal applications due to its high photocatalytic activity. Herein, we demonstrate hydrogenated TiO₂ nanofibers (H:TiO₂ NFs) with a core-shell structure prepared by the hydrothermal synthesis and subsequent heat treatment in hydrogen flow. H:TiO₂ NFs has excellent solar light absorption and photogenerated charge formation behavior as confirmed by optical absorbance, photo-Kelvin force probe microscopy and photoinduced charge carrier dynamics analyses. Photodegradation of various organic dyes such as methyl orange, rhodamine 6G and brilliant green is shown to take place with significantly higher rates on our novel catalyst than on pristine TiO₂ nanofibers and commercial nanoparticle based photocatalytic materials, which is attributed to surface defects (oxygen vacancy and Ti³⁺ interstitial defect) on the hydrogen treated surface. We propose three properties/mechanisms responsible for the enhanced photocatalytic activity, which are: (1) improved absorbance allowing for increased exciton generation, (2) highly crystalline anatase TiO₂ that promotes fast charge transport rate, and (3) decreased charge recombination caused by the nanoscopic Schottky junctions at the interface of pristine core and hydrogenated shell thus promoting long-life surface charges. The developed H:TiO₂ NFs can be helpful for future high performance photocatalysts in environmental applications.