BaFe12O19 single-particle-chain nanofibers have been successfully prepared by an electrospinning method and calcination process, and their morphology, chemistry, and crystal structure have been characterized at the nanoscale. It is found that individual BaFe12O19 nanofibers consist of single nanoparticles which are found to stack along the nanofiber axis. The chemical analysis shows that the atomic ratio of Ba/Fe is 1:12, suggesting a BaFe12O19 composition. The crystal structure of the BaFe12O19 single-particle-chain nanofibers Is proved to be M-type hexagonal. The single crystallites on each BaFe12O19 single-particle-chain nanofibers have random orientations. A formation mechanism is proposed based on thermogravimetry/differential thermal analysis (TG-DTA), X-ray diffraction (XRD), and transmission electron microscopy (TEM) at six temperatures, 250, 400, 500, 600, 650, and 800 degrees C. The magnetic measurement of the BaFe12O19 single-particle-chain nanofibers reveals that the coercivity reaches a maximum of 5943 Oe and the saturated magnetization is 71.5 emu/g at room temperature. Theoretical analysis at the micromagnetism level is adapted to describe the magnetic behavior of the BaFe12O19 single-particle-chain nanofibers.