Polymeric nanofibers are widely studied in the textile industry since with them, it is possible to get a great variety of functionalities. In this paper, polyamide 6/66 (PA 6/66) solutions at different concentrations (12, 17, and 22% wt) were made, to get nanofibers through the basic electrospinning process which were characterized by scanning electron microscope (SEM) and productivity. Afterwards, nanofiber bundles were produced using the electrospinning sol-gel process, which were characterized by SEM and tensile test. From the results of statistical optimization based on one-way analysis of variance (ANOVA) with post hoc Tukey HSD, it was found that nanofiber bundles with higher productivity (1.39 +/- 0.15 mg/min), draw ratio (9.0 +/- 1.2), and tensile strength (29.64 +/- 7.40 MPa) were obtained with a 17% concentration. Finally, a thermal characterization through differential scanning calorimetry (DSC) was done, finding evidence of a T-g and T-m reduction in the nanofibers in relation to PA 6/66 pellets and nanofiber bundles.