The aim of this study is to produce ultrafine fibers based on native yam starch as a polymeric material using the electrospinning technique. For this purpose, a 2³ multivariate design is used, with central and axial points in order to optimize the electrospinning operating conditions (source voltage, distance between the needle and the collector, and flow of the polymeric solution). The morphology and diameter of the ultrafine fibers are evaluated by scanning electron microscopy. The investigated responses are the average diameter of the fibers, the standard deviation of the average diameter, and the number of beads. The optimum condition for the production of ultrafine fibers is: voltage of 20 kV, distance between the needle and the collector of 20.5 cm, and flow of 1 mL h−1. With these conditions, it is possible to form fibers with an average diameter of 134.1 ± 16.71 nm, with homogeneous morphology, and without beads.