This present study demonstrates the development of high-performance polysulfone (PSf) hybrid mixed matrix membranes (MMMs) through the collaborative inclusion of multiwalled carbon nanotubes (CNTs) and reduced graphene oxide (rGO). The nanofillers are aligned by virtue of an AC electric field in order to formulate a multifunctional composite membrane structure for selective separation of O-2/N-2 gas. Proper alignment of the conducting nanofillers within PSf was confirmed by utilizing different microscopy and spectroscopy techniques. Hybridization of CNTS and rGO resulted in concurrent enhancement of permeability as well as the selectivity of the neat membrane. The inclusion of rGO nanosheets established a long, tortuous path hindering the permeation of gas molecules possessing the larger molecular size, while CNTs-filled MMM achieved better permeation due to their favorable intrinsic structural characteristics. The overall performance of the aligned hybrid membranes was found to be significant in contrary to single filler-based membrane systems (PSf /CNTs and PSf/rGO).