In this study, Polyvinyl alcohol (PVA) blended with Polyethylene glycol (PEG), Monosodium glutamate (MSG) and Glutamic acid (GA) was cast on a reverse osmosis membrane to form a composite membrane. It is expected that the ether group can increase the CO2 affinity of the membrane. Sodium tetraborate (Borax) as a crosslinker can increase membrane basicity and glutamic acid (salt) can provide an enhanced transport mechanism, thereby improving the permeability and selectivity of carbon dioxide. FTIR spectra show that the thickness of coating is sufficiently low, while SEM results show that PVA-PEG series have a dense surface, and particles are observed on the surface of MSG/GA series. The gas permeance and separation performance of the composite membrane was tested using a single gas. Results showed that CO2 had higher permeance (GPU) at lower pressure differential. PEG with an ether group had the greatest effect on improving CO2 permeance and selectivity. However, MSG and GA with amine groups could not effectively improve CO2 selectivity due to solubility. The best coating solution was provided by PVA-PEG-1.2. The CO2 selectivity of the composite membrane was 10.05 with a pressure differential of 1.00 bar in a humid environment and no obvious deterioration was observed over a 10-day period. Borax can improve selectivity, water absorption, and thermal stability while avoiding the need for high temperature and long crosslinking time of aldehydes, which makes it possible to be used in a PVA carbon dioxide separation membrane.