Differential scanning calorimetry (DSC) is a useful technique for analysing the thermal behaviour of materials by measuring the heat transferred through a sample during temperature fluctuations. For polymers, understanding their thermal characteristics is crucial to determine their process capability, mechanical properties, stability at high temperatures, and suitability for specific applications. In this context, the electrospinning process involves heating polymers and subjecting them to high voltage, leading to changes in their thermal properties. Therefore, it is essential to identify these modifications to determine the thermal conductivity, stability, and temperature management of the nanofiber for specific applications. This study focuses on the analysis of polyamide (PA6) nanofibers produced by electrospinning using DSC and compares them to virgin PA6 to identify significant changes in thermal properties. The PA6 nanofibers were prepared by electrospinning PA6 polymer and collecting on a rotating drum at a needle tip of 20 cm to the collector centre distance. For comparison of thermal properties, the same virgin PA6 was used for DSC testing from which nanofibers were produced. The results show that the nanofiber mat’s glass transition temperature increased by 3.2%, while the melting temperature decreased by 0.7%. Furthermore, the delta Cp (change in specific heat capacity) of the nanofiber mat was enhanced by 96%, and its thermal heat capacity and crystallinity increased by 16%. Therefore, this study provides insights into the alterations in the thermal characteristics of the nanofiber mat created by electrospinning.