A novel and simple organoselenium-involved 7-membered cyclization to access diverse seleno-benzo[b]azepines has been developed. This protocol involves an electrophilic cyclization process and is accomplished under mild conditions. Discussion of the mechanism rationalizes the regioselectivity observed in transformation. The studies of further transformation of seleno-benzo[b]azepines and large-scale experiment reveal the promising utility of this methodology.