Water-swollen hydrogel membranes are good candidates for CO2 separations due to the favorable solubility of CO2 in water. However, the excessive amount of water often causes the poor mechanical property and low selectivity. Herein, we propose a bioadhesion-inspired method to construct robust and high-performance CO2 separation membranes via in situ generation of polydopamine (PDA) nanoaggregates within poly (vinyl alcohol) (PVA) matrix. PDA nanoaggregates entangled with PVA chains and formed hydrogen bonding with hydroxyl groups from PVA chains. Physical cross-linking occurred between PVA chains and PDA nanoaggregates. Compared with the PVA membrane, the PVA-PDA hybrid membrane with the dopamine content of 0.5 mol% exhibited a 1.7-fold increase in tensile strength and a 2.2-fold increase in the tensile modulus. The membranes were used for CO2/CH4 separation. The physical cross-linking resulted in a PVA chain rigidification region around PDA nanoaggregates, which hindered the penetration of larger-size gas molecules and thus enhancing the CO2/CH4 selectivity. Moreover, the abundant amine groups from PDA nanoaggregates could facilitate CO2 transport. The optimized hybrid hydrogel membrane exhibited CO2/CH4 selectivity of 43.2, which was 43.85% higher than that of the PVA membrane. The bioadhesion-inspired method opens up new opportunities to exploit the potential application of hydrogel membranes.