The semiempirical methods of quantum chemistry are reviewed, with emphasis on established neglect of diatomic differential overlap‐based methods (MNDO, AM1, PM3) and on the more recent orthogonalization‐corrected methods (OM1, OM2, OM3). After a brief historical overview, the methodology is presented in nontechnical terms, covering the underlying concepts, parameterization strategies, and computational aspects, as well as linear scaling and hybrid approaches. The application section addresses selected recent benchmarks and surveys ground‐state and excited‐state studies, including recent OM2‐based excited‐state dynamics investigations.This article is categorized under: Electronic Structure Theory > Semiempirical Electronic Structure Methods