Amine-containing facilitated transport membranes can have both high permeability and selectivity due to the reversible reaction between CO 2 and amino groups for effective carbon capture from flue gas. We have developed an improved method for the synthesis of high-molecular-weight sterically hindered polyvinylamine (PVAm) as the new fixed-site carrier in thin-film composite membranes for CO 2 capture. Commercially available PVAm was N -monomethylated into poly- N -methyl- N -vinylamine (PVAm-CH 3 ) using the stepwise reductive amination with a highly polar fluorinated alcohol as the solvent to enhance the equilibrium shift to the formation of the imine intermediate. The method prevented over-alkylation, resulting in the increased yield of the target product. PVAm-CH 3 exhibited excellent CO 2 facilitation with a CO 2 permeability of 445.7 Barrer (1 Barrer = 3.349 × 10 −16 mol m m −2 s −1 Pa −1 ) and a CO 2 /N 2 selectivity of 70.3, which are above the Robeson 2008 upper bound. The PVAm-CH 3 solution retained a sufficiently high viscosity after incorporating the amino acid salt, 2-(1-piperazinyl)ethylamine sarcosinate (PZEA-Sar), as the mobile carrier for the membrane coating on nanoporous polyethersulfone (PES) substrates without any penetration issues. The resultant thin-film composite PVAm-CH 3 /PZEA-Sar membrane with a thickness of approximately 170 nm exhibited a superior CO 2 performance of 1071 GPU (1 GPU = 3.349 × 10 −10 mol m −2 s −1 Pa −1 ) and a CO 2 /N 2 selectivity of 183 at 57 °C and a feed gas pressure of 111.64 kPa (1.5 psig). This PVAm-CH 3 /PZEA-Sar membrane surpassed the latest redefined 2019 CO 2 /N 2 upper bound and outperformed other polymer-based membranes. Density functional theory calculations also demonstrated that PVAm-CH 3 showed a stronger preference, relative to PVAm, toward the more efficient bicarbonate pathway. Thus, the steric hindrance effect of PVAm-CH 3 enhanced the solubility of CO 2 in the polymer matrix and resulted in the higher CO 2 permeance. • Hindered polyvinylamine (PVAm-CH 3 ) synthesized using stepwise reductive amination. • The reaction conditions optimized for the highest N -methylation degree of 39%. • PVAm-CH 3 fixed-site carrier membrane exhibited excellent CO 2 facilitation. • The improved performance of PVAm-CH 3 was illustrated by DFT calculations. • A composite membrane showed 1071 GPU CO 2 permeance and 183 CO 2 /N 2 selectivity.