Mixed matrix membranes (MMMs) generally have some fatal defects, such as poor compatibility between the two phases leading to non-selective pores. In this work, PIM-1 was chosen as the polymer matrix, and UiO-66 modified with amidoxime (UiO-66-AO) was used as the filler to prepare the MMMs. In the MMMs, the amino and hydroxyl groups on UO-66-AO form a rich hydrogen bond network with the N and O atoms in the polymer PIM-1 chain to improve the compatibility between the polymer matrix and the filler. In addition, the selective adsorption of CO2 by the amidoxime group can promote the transport of CO2 in the membrane, which enhances the gas selectivity. The CO2 permeability and CO2/N2 selectivity of UiO-66-AO@PIM-1 MMMs are increased by 35.2% and 45.2% compared to pure PIM-1 membranes, reaching 7535.5 Barrer and 26.9, surpassing the Robeson Upper Bound (2008) and close to the 2019 Upper Bound. After 38 days of the aging experiment, the CO2 permeability is approximately 74% of the original. The results show that the addition of UiO-66-AO has an obvious effect on improving the aging properties of the membrane. The UiO-66-AO@PIM-1 MMMs have a bright prospect for CO2 separation in the future.