The main objective of the study was to investigate the interaction of starch and low-methoxylated pectin in the elaboration of electrospun fibers, verifying the hypothesis that the interaction of this polymer with starches from different botanical sources (arrowroot, cassava and sweet potato) allows the development of electrospun materials with distinct characteristics, using multivariate analysis methods to prove the hypothesis. The development of electrospun materials with pectin (0, 2, 6 and 10 %) allowed the production of nanometric and ultrafine fibers with diameters ranging from 156 to 465 nm for arrowroot starch fibers, 192–612 nm for cassava starch fibers and 136–446 nm for sweet potato starch fibers containing 0 and 10 % pectin, respectively. Infrared spectra indicated the formation of amorphous regions in the fibers, which were confirmed by X-ray diffraction. There was a loss of thermal stability and surface modifications with increasing pectin concentration. Principal Component Analysis indicated that the degree of esterification and the increase in pectin concentrations increased the average diameters of the materials. Hierarchical Cluster Analysis showed that three distinct fibers were obtained. Therefore, electrospun fibers of starch and low methyl esterified pectin were obtained with distinct characteristics dependent on the starch source.