The search for new superconductors capable of carrying loss-free current has been a research theme in condensed matter physics for the past decade. Among superconducting compounds, titanates have not been pursued as much as Cu 2+ (3d 9 ) (cuprate) and Fe 2+ (3d 6 ) (pnictide) compounds. Particularly, Ti 3+ -based compounds or electron systems with a special 3d 1 filling are thought to be promising candidates as high-T C superconductors, but there has been no report on such pure Ti 3+ -based superconducting titanates. With the advent of thin-film growth technology, stabilizing new structural phases in single-crystalline thin films is a promising strategy to realize physical properties that are absent in the bulk counterparts. Herein, we report the discovery of unexpected superconductivity in orthorhombicstructured thin films of Ti 2 O 3 , a 3d 1 electron system, which is in strong contrast to the conventional semiconducting corundum-structured Ti 2 O 3 . This is the first report of superconductivity in a titanate with a pure 3d 1 electron configuration. Superconductivity at 8 K was observed in the orthorhombic Ti 2 O 3 films. Leveraging the strong structureproperty correlation in transition-metal oxides, our discovery introduces a previously unrecognized route for inducing emergent superconductivity in a newly stabilized polymorph phase in epitaxial thin films.