Magnetic nanofibers were prepared by electrospinning polymer/metal solutions of poly(acrylonitrile) (PAN) with magnetite (Fe3O4) nanoparticles. At a mass ratio of PAN:magnetite of 2:1, the total solid content in the dimethyl sulfoxide (DMSO) solution was varied between 15 wt.% and 25 wt.%, which represents the limits of the spinnable range. The results show that the most homogeneous nanofiber mats were 21 wt.% solid contents. At 15 wt.% solid contents, a nano-membrane with some fibrous regions was produced. Nanofibers at 25 wt.% had a much larger and more inhomogeneous diameter. Nevertheless, the magnetic properties of all samples were very similar, indicating that the distribution of magnetite nanoparticles in the fibers is comparable in all samples. The results also suggested that the samples spun from solutions with near-ideal solid contents (19–21 wt.%) contain agglomerations of the nanoparticles inside the nanofibers.