<p>Hydrogenated titanium dioxide nanotube arrays (H-TiO₂ NTAs) were fabricated through hydrogen atmosphere annealing (600&#xa0;°C) of anodically synthesized TiO₂ NTAs. The H-TiO₂ NTAs achieves an area capacitance of 11.1 mF cm⁻² at a scan rate of 10&#xa0;mV&#xa0;s⁻¹, which is approximate eightfold improvement compared to the TiO₂ NTAs electrode (1.41 mF cm⁻²) under the same conditions. The H-TiO₂ NTAs provide a good support for depositing pseudocapacitive materials polypyrrole to form coaxial heterogeneous polypyrrole and H-TiO₂ nanotube hybrids (PPy/H-TiO₂). Electrochemical impedance spectroscopy results indicate that the hydrogenation improves the conductivity of the TiO₂ NTAs, thus achieving excellent electrochemical performance compared with PPy/H-TiO₂. Galvanostatic charge–discharge (GCD) analysis revealed that the PPy/H-TiO₂ and PPy/TiO₂ nanotube hybrids have specific capacitances of 873 and 309 F g⁻¹ at a current density of 0.5 A g⁻¹. Moreover, the observed capacitance retention of PPy/H-TiO₂ and PPy/TiO₂ nanotube hybrid is 87.7% and 79.4% at the current density of 20 A g⁻¹ after 10,000 cycles, respectively. These results confirm that hydrogenation-induced conductivity optimization in TiO₂ NTAs significantly amplifies the electrochemical activity of PPy composites. The synergistic combination of conductive H-TiO₂ substrates with pseudocapacitive PPy demonstrates superior potential for supercapacitor applications, highlighting the critical role of substrate engineering in hybrid electrode design.</p>