AbstractNitride perovskite LaWN3has been predicted to be a promising ferroelectric material with unique properties for diverse applications. However, due to the challenging sample preparation at ambient pressure, the crystal structure of this nitride remains unsolved, which results in many ambiguities in its properties. Here, the authors report a comprehensive study of LaWN3based on high‐quality samples synthesized by a high‐pressure method, leading to a definitive resolution of its crystal structure involving nitrogen deficiency. Combined with theoretical calculations, these results show that LaWN3adopts an orthorhombicPna21structure with a polar symmetry, possessing a unique atomic polarization along thec‐axis. The associated atomic polar distortions in LaWN3are driven by covalent hybridization of W: 5d and N: 2p orbitals, opening a direct bandgap that explains its semiconducting behaviors. The structural stability and electronic properties of this nitride are also revealed to be closely associated with its nitrogen deficiency. The success in unraveling the structural and electronic ambiguities of LaWN3would provide important insights into the structures and properties of the family of nitride perovskites.