Polymers are used in various applications due to their excellent properties of lightweight, low cost, flexibility, and chemical stability. However, use of polymers is limited in thermal applications due to their low thermal conductivity. To overcome this limitation, many studies have been conducted to improve the thermal conductivity of polymers. Electrospinning process is a popular and inexpensive method to fabricate nanofibers. This fabrication process can alter polymers’ internal structures such as crystallinity and molecular chain alignment, which can greatly affect thermal conductivity. Numerous nanofibers such as polyethylene, polyethylene oxide (PEO), polyethylene, polystyrene, and nylon were produced by electrospinning. These nanofibers exhibit significantly enhanced thermal conductivity compared to their bulk counterpart. In this study, we measure thermal conductivity of electrospun PEO/PEDOT:PSS nanofibers produced by varying electrospinning process parameters. We will discuss thermal conductivity variation on electrospinning process parameters and the relation between nanofiber’s internal structure and thermal conductivity.