A metastable bixbyite‐type polymorph of vanadium sesquioxide, V2O3, has recently been synthesized, and it transforms to the corundum‐type phase at temperatures around 550 °C. The possibility of a paramagnetic to canted antiferromagnetic or even spin‐glass‐like transition has been discussed. Quantum‐chemical calculations on the density‐functional theory level including explicit electronic correlation confirm the metastability as well as the semiconducting behavior of the material and predict that the bixbyite‐type structure is about 0.1 eV less stable than the well‐known corundum‐type phase. Nonetheless, quasiharmonic phonon calculations manifest that bixbyite‐type vanadium sesquioxide is a dynamically stable compound. Other possible V2O3 polymorphs are shown to be even less suitable candidates for the composition V2O3. © 2012 Wiley Periodicals, Inc.