Bonded type RE 3+ doped luminescent co-polymer was synthesized by solution free radical copolymerization. The influence of charge sequence, monomers and co-polymerized method on properties and structures of the co-polymers was studied. The emission intensity of the co-polymers at different RE 3+ concentrations was tested. The results showed that the co-polymers of Eu-PSt and Eu-PMMA both had wide absorption peak at 200–400 nm and the strongest peak appeared at 235 nm. The fluorescent intensity of Eu 3+ doped polystyrene copolymer was stronger than that of Eu 3+ doped PMMA copolymer. The characteristic emission of europium ions was observed in the co-polymers. The copolymer doped with rare earth elements showed the “sensitization effect” for the central ions. The bonded-type rare earth copolymer not only enhanced the energy transfer efficiency, but also improved the fluorescence intensity by increasing the rigidity of main and side chain.