The bottleneck of conventional polymeric membranes applied in industry has a tradeoff between permeability and selectivity that deters its widespread expansion. This can be circumvented through a hybrid membrane that utilizes the advantages of inorganic and polymer materials to improve the gas separation performance. The approach can be further enhanced through the incorporation of amine-impregnated fillers that has the potential to minimize defects while simultaneously enhancing gas affinity. An innovative combination between impregnated Linde T with different numbers of amine-functional groups (i.e., monoamine, diamine, and triamine) and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)-derived polyimide has been elucidated to explore its potential in CO2/CH4 separation. Detailed physical properties (i.e., free volume and glass transition temperature) and gas transport behavior (i.e., solubility, permeability, and diffusivity) of the fabricated membranes have been examined to unveil the effect of different numbers of amine-functional groups in Linde T fillers. It was found that a hybrid membrane impregnated with Linde T using a diamine functional group demonstrated the highest improvement compared to a pristine polyimide with 3.75- and 1.75-fold enhancements in CO2/CH4 selectivities and CO2 permeability, respectively, which successfully lies on the 2008 Robeson's upper bound. The novel coupling of diamine-impregnated Linde T and 6FDA-derived polyimide is a promising candidate for application in large-scale CO2 removal processes. © 2019 by the authors.