AbstractHere, highly‐oriented poly(m‐phenylene isophthalamide)/polyacrylonitrile multi‐walled carbon nanotube (PMIA/PAN‐MWCNT) composite nanofiber membranes with excellent mechanical strength and thermal stability are successfully produced using electrospinning. It is demonstrated that the cooperation of multi‐walled carbon nanotubes (MWCNT) and high‐speed rotating collection is beneficial to the acquisition of highly oriented fibers and effectively improves the mechanical strength of the membrane along the orientation direction. Specifically, the tensile stress of poly(m‐phenylene isophthalamide)/polyacrylonitrile (PMIA/PAN) membrane is enhanced significantly from 10.6 to 20.7 MPa, benefiting from the highly oriented alignment of the fibers as well as the reinforcing effect of MWCNTs on the fibers. Furthermore, the stressing process of single fiber and fiber aggregates is carefully simulated, and the influence of MWCNTs on the mechanical properties of PMIA/PAN‐MWCNT membranes is analyzed comprehensively, providing a meaningful auxiliary means for the study of mechanical properties. In addition, the composite nanofiber membrane has the advantages of both PMIA and PAN, possessing high temperature resistance, flame‐retardancy, and chemical stability, for an ideal high‐temperature material. In short, the as‐prepared PMIA/PAN‐MWCNT composite membrane with excellent comprehensive property emerges a promising application in many fields, especially in high‐tech.