Nylon 11 nanofibers mats were successfully prepared by electrospinning process from formic acid solution. The scanning electron microscopy (SEM) images showed that nanofibers with uniform diameter were produced when the polymer concentration was 10% w/v, whereas ribbons were formed at a higher concentration. The crystalline structure of the nanofibers mats was investigated using X-ray diffraction (XRD) and it was found that the nanofibers mats crystallized in gamma form. The melt crystallized as well as solution casted films however exhibited a form. The thermal properties of these samples were studied using differential scanning calorimetry (DSC) and it was observed that electrospun fibers showed higher crystallinity than the melt-crystallized samples. However, the crystallinity of electrospun fibers was lower than the solution-crystallized sample.