Abstract: Electrospinning of polyamides has been used for obtaining porous nanofibres that can be employed in a variety of applications; among them, their use for fabricating tissue scaffolds has attracted a lot of interest. In order to successfully apply these nanofibres in the biomedical field it is important to investigate the diverse parameters involved in this process. Fibre diameter, network morphology and mechanical properties are some of the most important features that can be tailored to mimic specific target tissues. Furthermore, crystallinity of the polymer is related to the mechanical response and biodegradability. This work aims to present a better insight into the structural understanding of fibres obtained from electrospinning process by evaluating the crystallinity percentage in polyamide 6,6 nanofibres obtained at different conditions. The parameters studied in this work are the solution concentration, flow rate, voltage applied and distance from the tip of the needle to the collector surface. Differential scanning calorimetry was used to determine the crystallinity of the samples. The morphology of the nanofibres was observed by scanning electron microscopy. The chemical structure of the nanofibres was analysed by infrared and Raman spectroscopies. The results obtained showed those parameters that were statistically significant on the crystallinity of the poplyamide 6,6 nanofibres.