Magnetic semiconductors are highly sought in spintronics, which allow not only the control of charge carriers like in traditional electronics, but also the control of spin states. However, almost all known magnetic semiconductors are featured with bandgaps larger than 1 eV, which limits their applications in long‐wavelength regimes. In this work, the discovery of orthorhombic‐structured Ti2O3 films is reported as a unique narrow‐bandgap (≈0.1 eV) ferromagnetic oxide semiconductor. In contrast, the well‐known corundum‐structured Ti2O3 polymorph has an antiferromagnetic ground state. This comprehensive study on epitaxial Ti2O3 thin films reveals strong correlations between structure, electrical, and magnetic properties. The new orthorhombic Ti2O3 polymorph is found to be n‐type with a very high electron concentration, while the bulk‐type trigonal‐structured Ti2O3 is p‐type. More interestingly, in contrast to the antiferromagnetic ground state of trigonal bulk Ti2O3, unexpected ferromagnetism with a transition temperature well above room temperature is observed in the orthorhombic Ti2O3, which is confirmed by X‐ray magnetic circular dichroism measurements. Using first‐principles calculations, the ferromagnetism is attributed to a particular type of oxygen vacancies in the orthorhombic Ti2O3. The room‐temperature ferromagnetism observed in orthorhombic‐structured Ti2O3, demonstrates a new route toward controlling magnetism in epitaxial oxide films through selective stabilization of polymorph phases. Epitaxial Ti2O3 (Ti3+: 3d1) thin films on Sapphire are systematically investigated, and, more interestingly, a new stabilized orthorhombic phase is fabricated. Depending on extensive physical and optical properties measurements, the new orthorhombic Ti2O3 is confirmed to be a narrow band‐gap (≈0.11 eV) n‐type semiconductor with emergent ferromagnetism, while the corundum Ti2O3 is a p‐type antiferromagnetic semiconductor with a trigonal structure.