<p>In present work, the oxidation of ferrocene (FeCp₂) to ferrocenium cation (FeCp₂⁺) was investigated on electrode consisting of nitrogen-doped multi-walled carbon nanotubes (N-MWCNTs) in acetone (ACE), acetonitrile (ACN), dichloromethane (DCM), and dimethyl sulfoxide (DMSO) in presence of <i>n</i>-tetrabutylammonium hexafluorophosphate (NBu₄PF₆) by means of cyclic voltammetry and electrochemical impedance spectroscopy. For comparison reasons studies of FeCp₂^+/0 on glassy carbon (GC) were carried out. Parameters such as, half-wave potentials (<i>E</i>_1/2), diffusion coefficients (<i>D</i>), heterogeneous electron-transfer rate constants (<i>k</i>_s), and charge-transfer resistances (<i>R</i>_ct) of FeCp₂^+/0 were determined. The electron-transfer process was found to be reversible and diffusion controlled on both electrodes in all investigated solvents. The <i>E</i>_1/2 values tend to shift towards less positive potentials with the increase of dipole moment and dielectric constant of solvent. Furthermore, both <i>D</i> and <i>k</i>_s values tend to decrease with the progressively increase of viscosity of solvent. In addition, the <i>k</i>_s values vary inversely with the <i>R</i>_ct parameters indicating that the charge-transfer kinetics is strongly affected by the impedance behavior of electrode. Among the electrodes probed, the N-MWCNTs-based film provides faster electrochemical process since it affords insignificant barrier for interfacial electron transfer. The lower limit of detection (<i>LOD</i>) estimated for N-MWCNTs (0.6 × 10^–6–3.6 × 10^–6&#xa0;mol∙L⁻¹) and GC (1.8 × 10^–6–6.2 × 10^–6&#xa0;mol∙L⁻¹) towards FeCp₂^+/0 was found to be strongly tied to the diffusion coefficient of redox system in different solvents.</p>