An effective method to study and predict the complex mechanism of electrospinning is needed. A combination of design of experiments (DOEs) and finer tuning of the experimental parameters were used to investigate the effect of individual and interactions of solution, electrospinning, and environmental conditions on the dimensions and morphology of polyacrylonitrile (PAN) nanofibers. Analyses on DOEs determined that solution viscosity, controlled by the concentration of polymer precursor, was the predominant factor in manipulating the PAN nanofiber diameter. Similarly, reduced surface tension controlled by the addition of surfactant contributed to smoother nanofibers. An appropriate applied voltage for stable formation of Taylor cone was established. DOE on environmental conditions revealed the absolute moisture content played a significant role in causing beads. A minimum polyacrylonitrile (PAN)‐based fiber diameter of 42±7 nm was achieved with solution containing 3.25 wt. % PAN, 0.1 wt. % BYK® surfactant in N,N‐dimethylformamide (DMF). PAN nanofibers were subsequently stabilized then carbonized. BET analysis of the carbonized nanofibers showed the specific surface area increased as a function of nanofiber diameter, reaching 684 m2/g at 407 nm. Preliminary results from the electrochemical characterization of the carbon nanofibers showed the double‐layer capacitance increased with decreasing fiber diameter, showing suitable potential for electrode applications.