The novel copolymerization polyimide (PI) hollow fibers (HFs) of 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) containing –CF3 groups were prepared and investigated through both simulation and experiment. To demonstrate the alteration attributable to the introduction of fluoromonomers, the condensed states of pyromellitic dianhydride (PMDA)/4,4′-oxybisbenzenamine (ODA), PMDA/6FDA/ODA, and 6FDA/ODA PI were constructed by Material Studio, and we simulated the mobility of molecular chain, free volume fraction, and O2/N2 dissolution–diffusion process. The molecular dynamics simulation results demonstrated that the properties of the copolymerized PI system with 6FDA were significantly improved, while the selectivity remained almost unchanged. Then, the films of copolymerized PI and HFs were prepared by the two-step method, and O2/N2 permeability of the PI copolymer films was characterized, indicating that although the gas permeation performance was greatly improved, the selectivity was not so satisfactory. However, the selection factor increased heavily after polydimethylsiloxane coating.