Mixed matrix membranes (MMMs) were fabricated by incorporating mesoporous silica-coated on multi-walled carbon nanotube (MWCNTs@mSiO2) core@shell filler into the Pebax(R) MH 1657 (Pebax) matrix to improve CO2 separation performance.The efficient CO2 transport pathways were constructed by homogeneous dispersion of MWCNTs@mSiO2 within MMMs.The combination of core layer (MWCNTs) and shell layer (mSiO2) exerted a favorable synergistic effect on the permselectivity.The extraordinary smooth inner walls of MWCNTs acted as the fast pathways to render high CO2 permeability,meanwhile the mesoporosity of mSiO2 acted as the selective pathways to render high CO2/gas selectivity in MMMs.Thus,the constructed efficient pathways in MMMs led to the increases in both CO2 permeability and CO2/gas selectivity.The CO2 separation performance of Pebax-MWCNTs@mSiO2 membrane with 10 wt.% filler loading closed to the 2008 Robeson upper bound line.