The synthesis of π-extended pyrene-based luminescent compounds containing two six-membered phosphacycles has been realized through a two-step synthesis. It involves a Cu(II)-mediated double cyclization of tertiary diphosphane derivatives to afford dicationic molecules with quaternized phosphorus centers. Subsequent transformation of diphosphonium species into the corresponding P-oxide derivatives has been successfully achieved through Pd(0)-assisted cleavage of the P-Ph bonds, which opens a promising way for the functionalization of polyaromatic P-systems.