The unprecedented 2,2'-bis(azaphosphindole) has been synthesized via a new route. Reaction with NaH afforded a dianion derivative 5, which is easily transformed to alkylated bis(azaphosphindole) or (Z)-P,P,N,N-cisoid diazadiphosphafulvalene. The reaction features good regioselectivity and high steroselectivity. Relatively strong fluorescence is observed with diazadiphosphafulvalenes. The X-ray crystal structure analysis showed that dianion ligand 5 is bonded to two Na atoms in a bridging cis-fashion, which allows the synthesis of diazadiphosphafulvalene in a highly stereoselective approach.