The aim of this research is to investigate the effects of different molecular structures on the polyamide electrospun nanofibers. Polyamide 6, polyamide 6.6 are widely used in conventional textiles and polyamide 4.6 is a unique polymer for its properties suitable for engineering applications. Polyamide pellets were dissolved in formic acid and electrospun in different concentrations using a single nozzle electrospinning machine. The surface properties of these nanofibers were inspected in SEM and fiber diameters were measured. Thermal inspections were conducted using DSC. Surface tension and mechanical properties were also investigated. The data obtained from the study were compared to evaluate the changes in the fiber diameter, tensile strength, surface tension and thermal characterization of these three polymers in nano scale. As a result, it was concluded that Polyamide 4.6 had the most superior structural and crystallinity properties to produce nanofibers among the three polyamides investigated.