Single‐walled carbon nanotubes (SWCNTs) that have a reproducible distribution of chiralities or single chirality are among the most competitive materials for realizing post‐silicon electronics. Molecular doping, with its non‐destructive and fine‐tunable characteristics, is emerging as the primary doping approach for the structure‐controlled SWCNTs, enabling their eventual use in various functional devices. This review provides an overview of important advances in the area of molecular doping of structure‐controlled SWCNTs and their applications. The first part introduces the underlying physical process of molecular doping, followed by a comprehensive survey of the commonly used dopants for SWCNTs to date. Then, it highlights how the convergence of molecular doping and structure‐sorting strategies leads to significantly improved functionality of SWCNT‐based field‐effect transistor arrays, transparent electrodes in optoelectronics, thermoelectrics, and many emerging devices. At last, several challenges and opportunities in this field are discussed, with the hope of shedding light on promoting the practical application of SWCNTs in future electronics.