A facile and efficient method of inducing nanofibers of thermosetting resins by electrospinning has been established. The study involves extensive exploitation of unconventional parameters of electrospinning, viz, temperature ranging from 10 to 40 degrees C, humidity of 19 and 75% RH, concentration and type of catalyst (0.1 N NaOH and 0.1 N hexamine), that affect the morphology of the fibers and a clear comparison using FESEM imaging. The instability of resorcinol formaldehyde toward electrospinning has been overcome by introducing a core-sheath approach using 10% PVA solution in a 1:1 ratio, pertaining to the molecular migration by the virtue of presence of charged ions with a core of 345 nm and a 108 nm shell. Thus-formed fibers can be carbonized to generate carbon fibers with high carbon yield and better dimensional stability to find potential in next-generation heat exchangers and chillers.