Macromolecules chain transfer agents (MCTA) were synthesized through the reversible addition fragmentation chain transfer polymerization (RAFT) by using S-l-Dodecyl-S′-(α, α′-dimethyl-α-acetic acid) trithiocarbonate(MTTCD), S, S′-bis (2-hydroxyethyl-2′-dimethylacrylate) trihiocarbonate (BDATC), 2-cyanoprop-2-yl dithiobenzoate (CPDB) as the chain transfer agents, methacrylamide (MAM) as the first polymerization monomer. The results showed that the structures of the end-group of dithiocarbamates had significant effects on the activity of dithiocarbamates for the polymerization of PMAM. The derived block copolymer (PMAM-b-PNVP) was prepared by using the above mentioned polymer as macromolecular RAFT agent and NVP as the second polymerization monomer. N-vinyl-γ-sodium aminobutyrate-sodium methacrylate copolymer (VSA-MSA) containing -NH2 and -COOH as the CO2 facilitated carrier, a kind of new fixed carrier membrane material for CO2 separation, was synthesized by hydrolysis of the resulted PMAM-b-PNVP. The chemical composition and structure of PMAM-CTA, PMAM-b-PNVP, MSA-VSA were analyzed by FTIR, 1HNMR and DSC, the molecular weight and polydispersity index were analyzed by GPC. The Relative molecular mass of polymer was controllable. The polydispersity index (1.2~1.3) of the obtained polymer was narrow via using MTTCD and BDATC. The VSA-MSA/PS composite membranes were prepared. The CO2 and N2 permeation performance were tested at different pressure. The results showed that the resulted composited membrane had a CO2 permeation rate of 1.2×10-4 cm3 (STP) cm-2s-1cmHg-1 and a N2 permeation rate of 8.57×10-7 cm3 (STP) cm-2s-1cmHg-1 and an ideal CO2/ N2 selectivity of 140.02 at a feed gas pressure of 7.6 cmHg and 30 °C.