Reported here is the first hexagonal perovskite oxynitride BaWON₂, which shows a polar 6H polytype. Synchrotron X‐ray and neutron powder diffraction, and annular bright‐field in scanning transmission electron microscopy indicate that it crystalizes in the non‐centrosymmetric space group P6₃mc, with a total order of nitride and oxide at two distinct coordination environments in cubic and hexagonal packed BaX₃ layers. A synergetic second‐order Jahn–Teller effect, supported by first principle calculations, anion order, and electrostatic repulsions between W⁶⁺ cations, induce large distortions at two inequivalent face‐sharing octahedra that lead to long‐range ordered dipoles and spontaneous polarization along the c axis. The new oxynitride is a semiconductor with a band gap of 1.1 eV and a large permittivity.