Temperature is an important parameter during electrospinning, and virtually, all solution electrospinning processes are conducted at ambient temperature. Nanofiber diameters presumably decrease with the elevation of working fluid temperature. The present study investigated the influence of temperature variations on the formation of polymeric nanofibers during single-fluid electrospinning. The surface tension and viscosity of the fluid decreased with increasing working temperature, which led to the formation of high-quality nanofibers. However, the increase in temperature accelerated the evaporation of the solvent and thus terminated the drawing processes prematurely. A balance can be found between the positive and negative influences of temperature elevation. With polyacrylonitrile (PAN, with N,N-dimethylacetamide as the solvent) and polyvinylpyrrolidone (PVP, with ethanol as the solvent) as the polymeric models, relationships between the working temperature (T, K) and nanofiber diameter (D, nm) were established, with D = 12598.6 − 72.9T + 0.11T
2 (R = 0.9988) for PAN fibers and D = 107003.4 − 682.4T + 1.1T
2 (R = 0.9997) for PVP nanofibers. Given the fact that numerous polymers are sensitive to temperature and numerous functional ingredients exhibit temperature-dependent solubility, the present work serves as a valuable reference for creating novel functional nanoproducts by using the elevated temperature electrospinning process.