The choice of current collector substrate plays a critical role in determining the electrochemical performance of supercapacitor electrodes. In this study, cobalt ferrite (CoFe2O4) nanoparticles were synthesized via a solution combustion method and employed as active materials for supercapacitor electrodes. Two types of conductive substrates—nickel foam and carbon paper—were systematically investigated to evaluate their influence on the electrochemical behavior of CoFe2O4-based electrodes. Electrodes were fabricated using identical slurry composition and deposition protocols to ensure fair comparison. Electrochemical measurements including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) were conducted in a three-electrode configuration. The results reveal that electrodes supported on nickel foam exhibited approximately 20% higher specific capacitance compared to those using carbon paper, along with improved charge transfer kinetics and reduced internal resistance. This enhancement is attributed to the three-dimensional porous structure and superior electrical conductivity of the nickel foam, which facilitate efficient electron transport and electrolyte accessibility. These findings highlight the importance of substrate selection in optimizing the performance of transition metal oxide-based supercapacitor electrodes and provide guidance for the rational design of advanced energy storage systems.