Considering both molecular sieving effect and compatibility of filler-polymer interface, the main challenges in the fabrication of excellent mixed matrix membranes (MMMs) are the selection of fillers. Here, porous organic polymer (POP) is chosen as fillers to fabricate a series of novel PIM-1 based MMMs for CO2 separation. TPFC-based POPs showed highly selective CO2 adsorption capacity and good interfacial compatibility with PIM-1 matrix. Moreover, amine modified POPs in MMMs can provide specific transfer chains for facilitating CO2 molecules separation. As a result, the obtained PIM-TPFC-CH2NH2 MMM exhibited excellent CO2 permeability of 7730 barrer and selectivity of 45.9 and 36.4 for CO2/N-2 and CO2/CH4 gas pairs, far beyond the 2008 Robeson upper bound and surpassed most reported state-of-the-art MMMs.