Fibrous mats were prepared by electrospinning of polyacrylamide-graft-polyaniline copolymers (PAAm-g-PANI) in a mixed solvent of water–dimethylformamide. The grafted copolymers were synthesized by oxidative polymerization of aniline in the presence of polyacrylamide; the effect of aniline/polyacrylamide ratio on the morphology of the fibrous mats and on their electrochemical properties was investigated. The composition and chemical structure of the copolymers were verified with FTIR. Polyaniline content higher than 40 wt% leads to the lack of electrospinability of the corresponding solutions. With polyaniline concentration increasing from 20 to 40 wt%, the fiber diameter decreases from 569 to 248 nm. WAXD study shows that the reflections from polyaniline crystallites are preserved during swelling, and the increasing polyaniline content results in the decreased sample compatibility with water. Galvanostatic charge–discharge, cyclic voltammetry by Trasatti method, and BET measurements reveal that most part of the charge in PAAm-g-PANI fibrous mats is stored via the pseudocapacitance mechanism. Maximum attained capacitances measured at 0.3 A g⁻¹ were 102 F g⁻¹ for the whole mass of electrode and 255 F g⁻¹ for the mass of the active material.