Conductive polymers such as PANI and conductive nanoparticles such as CNTs have very important effects on the polymer matrix. Although there are many studies carried out for just only PANI filler or carried out for just only CNT filler, there are no studies performed to see the synergistic effects of both PANI and functionalized CNTs on polymer matrix. Thus in this study, for the first time, PANI together with CNTs has been used as a filler for polymer matrix, polyacrylonitrile. It has been seen that the diameters of nanofibers increase due to presence of PANI and CNTs and the effect of PANI on the increase in diameter is higher than that of CNTs. An increase in filler content results in an increase in agglomeration risk which degrades the properties of composite nanofiber web. However, higher breaking strength is obtained for the composite nanofiber with 1% CNT and 3% PANI. Insulator PAN became an antistatic material (static dissipative material) by the presence of CNT and PANI. However, an increase in filler content did not increase the electrical conductivity. This may be due to the agglomeration and void formation around the filler which destroy the network leading to the decrease in conductivity. Presence of PANI and CNT increases the crystallinity of PAN. The crystallinity of composite nanofiber with both of CNT and PANI is higher than that of pure PAN nanofiber, nanofiber with PAN, CNT and nanofiber with PAN, PANI. PANI increases the cyclization temperature and decreases the enthalpy; however CNT has a tendency to increase both the cyclization temperature and the enthalpy. When both of them (CNT and PANI) are present in high amount (3%), then both cyclization temperature and enthalpy decrease.