A new method to access sulfonated dibenz[b,e]azepines via visible‐light photoredox catalysis is described. Employing inexpensive and commercially available sulfonyl chlorides to form the sulfonyl radicals enables the alkyne addition reaction followed by a 7‐membered radical cyclization step to furnish sulfonated dibenzazepines. In addition, an Ugi‐type multicomponent reaction (MCR) for the synthesis of o‐aminophenylacetylene derivatives can also be used as a rapid substrate synthesis method for the cascade radical cyclization protocol to obtain a series of highly functionalized sulfonylated dibenzazepines, which undoubtedly greatly simplifies the synthetic steps of the dibenzazepine compounds that are important core structures in pharmaceuticals.