The growing demand for sustainable energy solutions highlights the need for advancements in electrocatalysts for direct methanol fuel cells (DMFCs). This study introduces a novel approach to enhance the efficiency and durability of nickel sulfide (NiS) catalysts. We developed a hierarchically porous structure integrated with reduced graphene oxide (rGO) on a nickel foam substrate. Using a dynamic hydrogen bubble template (DHBT) technique, we created a porous nickel scaffold. We then electrodeposited graphene oxide and NiS onto this scaffold, resulting in a hybrid structure termed NiS-rGO-Ni/NF. Characterization through SEM, XRD, and XPS confirmed that the catalyst has a highly porous structure with uniformly distributed Ni₃S₂ and Ni₃S₄ phases. The NiS-rGO-Ni/NF catalyst showed significant improvements over conventional NiS/NF. It achieved a peak current density of 84.10 mA/cm² in the presence of 0.1 M methanol, compared to 30.32 mA/cm² with NiS/NF. This enhancement is due to the porous nickel layer created using DHBT and the integration of rGO. Additionally, the NiS-rGO-Ni/NF catalyst demonstrated superior reaction kinetics, evidenced by a decrease in the Tafel slope from 204 mV/dec to 122 mV/dec. It also exhibited a remarkable increase in the electrochemically active surface area, reaching 179 cm² compared to 22 cm² for NiS/NF. These improvements in surface area and kinetics contribute to its excellent stability, with the catalyst maintaining consistent performance over 20 h of continuous operation. These results underscore the effectiveness of the NiS-rGO-Ni/NF catalyst in methanol oxidation and its potential for more efficient and stable electrochemical applications.