Synthesis of fibers from the waste of polyvinyl chloride (PVC) has been successfully done using electrospinning method. The PVC solutions were made with the solvents N, N dimethylformamide (DMF), tetrahydrofuran (THF) and dimethylacetamide (DMAc). The effects of PVC concentration on the morphology and the diameter of fibers were observed. The morphological change from particles to fibers took place along with the increasing concentration of PVC in DMF, DMAc, and THF. When DMF was used as the solvent, the average particle diameter was 2.91 μm for the concentration of 5 wt%. As the concentration was increased to 10 wt%, 15 wt%, and 20 wt%, fibers were obtained, and their mean diameters were 1.12, 1.47, and 1.63 μm, respectively. When DMAc was used, the average particle made of the precursor solutions of concentrations of 5 wt%, 10 wt%, and 15 wt% were 2.79 μm, 3.03 μm, and 3.31 μm, respectively. If the concentration was further increased to 20 wt%, then fibers were formed with the average diameter of 1.35 μm. Finally, with the use of THF solvent, the average particle diameters were 6.83 μm and 8.38 μm for the solution concentrations of 5 wt% and 10 wt%, respectively. When the concentrations were 15 wt% and 20 wt%, fibers were finally achieved with the average diameter of 1.38 μm and 2.83 μm, respectively. It was clearly found that there is a PVC critical concentration for a morphological transition from PVC particles to fibers.