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This paper reports the synthesis of CTAB mediated CSA doped PANI and GN/GNP@ PANI composite na-nofibers. The as synthesized composite nanofibers were examined by TEM, SEM, XRD, Raman spectro-scopy;UV–visible diffused reflectance spectroscopy and TGA. The CTAB mediated CSA doped composite nanofibers showed 59% higher DC electrical conductivity at ambient temperature than that of PANI, which might be due to the enhancement in the mobility of the charge carriers and reduction in hopping distance in the composite system. The CTAB mediated CSA doped composite nanofibers compared to PANI was observed to be showing enhanced DC electrical conductivity retention after various cycles of heating, suggesting an enhancement in thermal stability of the composite structure, which could be attributed to the synergistic effect of GN, GNP and PANI. Additionally, the composite nanofibers showed greater electrochemical activity and better capacitive performance and reduced optical bandgap than that of PANI.