We developed an in-situ iodination of organoarsenic homocycles for facile and general As-C bond formation. Quantitative in-situ generations of arsenic diiodides from organoarsenic homocycles and iodine were confirmed by (HNMR)-H-1 analysis. 9-Phenyl- and 9-methyl-9-arsafluorenes were prepared by this method and their optical properties were studied.