Mizoroki-Heck coupling polymerization of diiodonated 1,1'-binaphthyls ((S)-1/2) with divinylbenzenes (DVB-H/-Me/-OMe) afforded a series of poly(arylene vinylene ketone)s (PAVK1-PAVK6). The resulting PAVKs have high thermal stabilities, excellent solubilities in organic solvents, and pale blue to green fluorescence properties.