A group of low-Tg photorefractive polymers of double function with carbazole and p-nitrodiazencarbazole called P-2, P-3 and P-4 were synthesized by means of different proportional diazonium salts being diazo-coupled with the poly ［bis(6-carbazolhexyloxy)］ phosphazene(P-1). P-2, P-3 and P-4 were characterized by 31P NMR, 1H NMR, IR, UV-Vis, GPC, TG and DSC. The result showed that P-2, P-3 and P-4 have good heat stability (Td≈300 ℃) and a lower glass transition temperature (Tg≈30~40 ℃). Their fluorescence properties were studied by photoluminescence and the result showed that P-1 has a stronger fluorescence properties and fluorescence intensity. P-2, P-3 and P-4 have varying degrees of quenching after nitro joining. The fluorescence properties were related with numbers of carbazole and nitro and their molecular space structure.