In the electrospinning process, a modified parallel electrode method (MPEM), conducted by placing a positively charged ring between the needle and the parallel electrode collector, was used to fabricate highly aligned carbon nanotubes/polyacrylonitrile (CNTs/PAN) composite nanofibers. Characterizations of the samples-such as morphology, the degree of alignment, and mechanical and conductive properties-were investigated by a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM), universal testing machine, high-resistance meter, and other methods. The results showed the MPEM could improve the alignment and uniformity of electrospun CNTs/PAN composite nanofibers, and enhance their mechanical and conductive properties. This meant the successful preparation of highly aligned CNT-reinforced PAN nanofibers with enhanced physical properties, suggesting their potential application in appliances and communication areas.