In this study, we demonstrate a facile and cost-effective way to synthesize Nd-Fe-B of various shapes such as powders, rods and fibers using electrospinning, heat-treatment and washing procedures. Initially Nd-Fe-B fibers were fabricated using electrospinning. The as-spun Nd-Fe-B fibers had diameters ranging 489 to 630 nm depending on the PVP concentration in reaction solutions. The different morphologies of the Nd2Fe14B magnetic materials were related to the difference in thickness of the as-spun fibers. The relationships between the as-spun fiber thickness, the final morphology, and magnetic properties were briefly elucidated. The intrinsic coercivity of Nd2Fe14B changed with the change in morphology from powder (3908 Oe) to fiber (4622 Oe). This work demonstrates the effect of the Nd-Fe-B magnetic properties with morphology and can be extended to the experimental design of other magnetic materials.