Efficient electrocatalysts, with high tolerance to methanol oxidation, good stability, and acceptable cost are the main requisites for promising direct methanol fuel cell (DMFC) electrode materials. This target can be achieved by the integration of different active materials with unique structures. In this work, a cobalt metal–organic framework (Co-MOF) flower structure was prepared by a hydrothermal method, and then a simple ultrasonication method was employed to anchor carbon nanotubes (CNTs) in between the MOF flower petals and fabricate a Co-MOF/CNT hybrid composite. Different ratios of CNTs were used in the composite preparations, namely 25, 50, and 75 wt% of the composite. The nanocomposites were entirely investigated using different characterization techniques, such as XRD, FTIR, SEM, TEM, and XPS. Comparative electrochemical measurements confirmed that due to the integration of highly conductive CNTs with the porous active fascinating structure of Co-MOF, Co-MOF/50% CNTs exhibited improved electrocatalytic activity with a current density of 35 mA cm⁻² at a potential of 0.335 V and a scan rate of 50 mV s⁻¹. The excellent electrochemical activity and stability could be due to the synergy between Co-MOF and the CNTs that conferred adequate active sites for methanol electro-oxidation and a lower equivalent series resistance, as revealed from the electrochemical impedance spectroscopy study. This study opens a new avenue to decrease the utilization of platinum and increase the methanol oxidation activity using low-cost catalysts.