Background: Conjugated microporous polymers (CMPs) have been applied widely in several energy storage applications. Triphenylamine derivatives are good electrode materials that can be processed into SC devices because of their high charge mobilities, unique electronic properties, and high redox activity. Methods: We prepared two novel tetrabenzonaphthalene-linked conjugated microporous polymers (TBN-pH CMPs) through [4 + 2] and [4 + 3] Schiff-base condensations of 2,7,10,15-tetra(4-formylphenyl)tetrabenzonaphthalene (TBN-PhCHO) with tetrakis(4-aminophenyl)ethene (TPE-4NH2) and tris(4-aminophenyl)amine (TPA-3NH2), respectively. Fourier transform infrared, and solid-state 13C NMR spectroscopy investigated the structures of the as-prepared CMPs. Significant Findings: These CMPs, had large surface areas and outstanding thermal stability at temperatures of up to 400 ◦C, making them suitable for use as electrodes in supercapacitor (SC) systems. Indeed, the TBN-TPA CMP–based electrode had high specific capacitances (251 F g − 1 measured at 0.5 A g–1 ) and capacity retentions (94%, measured after 5000 cycles at 10 A g–1 ) when tested in three-electrode systems. We attribute the remarkable electrochemical activity and conductivity of the TBN-TPA CMP electrode to its large specific surface area (230 m2 g–1 ) and chemical structure featuring stacking of the benzene rings of its redox-active triphenylamine moieties.