In the present study, the effects of different dopants such as camphorsulfonic acid (CSA), dodecylbenzene sulfonic acid (DBSA) (70wt% in isopropanol), and dodecylbenzene sulfonic acid sodium salt (DBSANa(+)), and different solvents such as N-methylpyrrolidone (NMP), and N,N-dimethylformamide (DMF) on the structure and properties of polyacrylonitrile (PAN)/polyaniline (PANI) composite nano/microfiber web produced by the electrospinning technique have been investigated and compared to each other. It has been observed that the nano/microfibers produced from NMP solvent generally had larger fiber diameters than the nano/microfibers produced from DMF, while the use of DBSANa(+) resulted in the formation of larger diameters in comparison to other dopants. The use of NMP as the solvent resulted in higher breaking stress values for the reference samples and the composite samples, which contained CSA-doped PANI while the samples that contained DBSA(iso) and DBSANa(+)-doped PANI showed lower breaking stress values when electrospun from NMP. While the solutions prepared using DBSANa(+) showed higher solution conductivities, the use of NMP as the solvent resulted in lower solution conductivity values. Higher conductivity values were obtained with CSA in NMP and with DBSA(iso) in DMF. The conductivity values of the composite nano/microfiber webs were around 10(-8) and 10(-9)S/cm, which is the range for antistatic materials instead of insulator materials as pure PAN.