The design and development of strategies and catalysts are essential for sustainable energy production, particularly for the hydrogen evolution reaction (HER). Precious Pt/C catalyst is known to demonstrate high efficiency in the electrochemical HER and suffers from commercialization issues. Therefore, precious-metal-free and organic-based catalysts are of importance for a future perspective. In this work, cobalt tetra [4-[2-(1H-benzimidazol-2-yl)phenoxy]]phthalocyanine (CoTBImPc) is synthesized for the first time and characterized by physicochemical and electrochemical techniques. 1 H NMR and mass spectral data reveal the successful formation of the ligand and complex, whereas the thermogravimetry (TG) study confirms the thermal stability of the complex up to 400 °C. The electroactivity of CoTBImPc is compared with the hybrid composite of a carbon nanotube (CNT-CoTBImPc) and benchmark Pt/C catalyst for the HER. Linear sweep voltammetry (LSV) shows that an onset potential for the HER for CoTBImPc-CNT/GCE is shifted to a higher potential than that of CoTBImPc/ GCE, suggesting that the HER is more feasible at the surface of CoTBImPc-CNT. Higher activity for CoTBImPc-CNT/GCE in comparison with that of CoTBImPc/GCE in 0.5 M H 2 SO 4 (pH = 0.3) may be ascribed to the enhanced conductivity, a greater number of active sites, and a larger surface area. The hybrid composite yields a current density of −10 mA•cm −2 and demonstrates HER activity at a lower overpotential (63 mV). The benchmark Pt/C catalyst and the as-synthesized pristine phthalocyanine molecule exhibit the HER at overpotentials of 3 and 160 mV, respectively, at a current density of −10 mA•cm −2 . A lower Tafel slope value of 43.2 mV•dec −1 and a higher double-layer capacitance value of 44 mF•cm −2 confirm that the hybrid composite is one of the superior catalyst candidates for the HER compared to the bare glassy carbon electrode (GCE) and pristine metal phthalocyanine. Further, CoTBImPc-CNT/GCE also exhibits an excellent stability during the HER.