Polyaniline (PAni)/B-doped diamond/carbon fiber (CF) ternary composites were produced and characterized, aiming their application as electrodes for supercapacitor device. In order to optimize the composite properties, structurally different CF substrates, heat treated at 1000 and 2000°C, were used to grown diamond films. Moreover, the diamond films were grown on CF in two different morphologies, boron doped micro and nanocrystalline diamond (BDD/BDND), by Hot Filament Chemical Vapor Deposition (HFCVD) technique. FEG-SEM images showed that PAni covered and enwrapped the diamond/CF surfaces, producing tridimensional electrodes. Raman spectra confirmed the PAni formation for all composites. Electrochemical characterizations indicated that the PAni/BDD/CF2000 composite has the highest current density and capacitance response among the studied composites combinations. In addition, it showed the most reversible oxidation and reduction processes, the greatest charge storage capacity as well as the lowest charge transfer resistance.