A facile approach for the synthesis of substituted iodo-benzo[a]phenazines from 2-aryl-3-(aryl/alkylethynyl)quinoxalines via 6-endo-dig ring closure has been described under mild reaction conditions. Iodocyclization proceeds through the iodonium ion intermediate followed by nucleophilic cyclization with the C-H bond of the arene. Furthermore, the resulting 6-iodo-5-aryl/alkyl benzo[a]phenazine derivatives allowed for structural diversification by employing various coupling reactions. The structure of iodo-benzo[a]phenazine was confirmed by X-ray crystallographic studies of the compound.