The utility of polymers in the fabrication of nanofibers via electrospinning is well established. Paramount to their application is understanding of their thermal properties, as these dictate not only their processability but also their mechanical robustness, stability under elevated temperatures, and suitability for intended applications. The electrospinning process, which involves heating polymers and subjecting them to high voltage, inherently modifies their thermal characteristics. This study attempts to elucidate these alterations, particularly by focusing on polyacrylonitrile (PAN) nanofibers. Employing techniques such as thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC), the study compares the thermal properties of electrospun PAN nanofiber mats with those of their virgin counterparts. The PAN nanofibers were synthesised by electrospinning the PAN polymer solution and collecting the resultant mat on a flat plate collector. For a comparative analysis, virgin PAN, from which nanofibers were derived, underwent identical thermal testing. The findings reveal a reduction in the glass transition temperature of PAN nanofibers by approximately 3-5% compared to virgin PAN. In addition, a significant reduction in heat capacity of about 42% was observed in the nanofibers. Additionally, the TGA results indicated solvent evaporation at approximately 110 ° C. Therefore, this investigation sheds light on the nuanced alterations in the thermal characteristics of PAN nanofiber mats as a result of the electrospinning process, providing vital insights for their application in various thermal management scenarios.