Unlike conventional routes by van der Waals forces, a facile and novel approach using covalent bonding is established in the present work to synthesize polyaniline (PANI)-grafted carbon nanofiber (CNF) composites as promising supercapacitors. For this purpose, toluenediisocyanate was initially functionalized to carboxylated CNF via amidation followed by reaction with excess aniline to form a urea derivative and residual aniline, which was subsequently polymerized and grafted with a urea derivative. Amidation of CNF (TCNF) and, consequently, the grafting of PANI on TCNF were verified by IR, Raman, 1H NMR, X-ray photoelectron, and UV-visible spectroscopic methods, X-ray diffraction, and thermogravimetric analysis. Morphological analysis revealed uniform distribution of PANI on the surface of TCNF, indicating strong interaction between them. Electrochemical tests of the composite containing 6 wt % TCNF demonstrated efficient capacitance of ∼557 F g(-1) with a capacity retention of 86% of its initial capacitance even after 2000 charge-discharge cycles at a current density of 0.3 A g(-1), suggesting its superiority compared to the materials formed by van der Waals forces. The remarkably enhanced electrochemical performance showed the importance of the phenyl-substituted amide linkage in the development of a π-conjugated structure, which facilitated charge transfer and, consequently, made it attractive for efficient supercapacitors.