Fibers of poly(lactic acid) (PLA) blended with p‐toluenesulfonic acid‐doped polyaniline, PAni.TSA, were obtained by electrospinning, following a factorial design which was used mainly to study the effect of four process parameters (PLA solution concentration, PAni solution concentration, applied voltage, and flow rate) on fiber diameter. Due to the non‐Gaussian spread of the fiber diameters, probability density functions (PDF's) were used to describe them, and the main effect analysis was performed considering the most representative values of these PDF's. This study suggests that the main factor which governs the fiber dimension is the concentration of the PAni solution and its synergy with the others factors. Furthermore, in spite of the high complexity of the electrospinning process, the statistical model was able to describe the process with 95% confidence, therefore enabling one to precisely predict fiber diameter. Nanofiber formation was simulated using the results of the experimental design and validation tests were performed to minimize the fiber diameter.
