a b s t r a c tPoly(amidoamine) (PAMAM) dendrimers are physically immobilized in a crosslinked poly(ethylene glycol) (PEG) upon photopolymerization of PEG dimethacrylates (PEGDMAs) in the presence of the dendrimers in ethanol. The dendrimer-containing polymeric membranes exhibit excellent CO 2 separation properties over smaller H 2 . However, immiscibility of PEG matrix and the dendrimer results in the formation of a bicontinuous phase-separated structure on a couple of microns scale, which inhibits to reduce the membrane thickness for enhancement of the CO 2 permeability. A compatible crosslinker, 4GMAP, is developed from the dendrimer and glycidyl methacrylate. Incorporation of the compatible crosslinker in the photopolymerization suppresses the macrophase separation between PAMAM dendrimer and PEG matrix and allows preparation of polymeric membranes as thin as 10 μm with high CO 2 selectivity. The 4GMAP incorporation also endows pressure tolerance by increasing crosslinking density of the resulting polymeric membranes. The CO 2 permeance is elevated from 9.94 Â 10 À 13 to 1.68 Â 10 À 11 m 3 (STP) m À 2 s À 1 Pa À 1 , by reducing the membrane thickness from 640 to 9.5 μm with 10 of CO 2 selectivity at 313 K and 0.56 MPa of CO 2 partial pressure.