Mesoporous graphene (MG) synthesized via a facile hydrothermal method using soft‐template, triblock copolymer P123 and graphene oxide was utilized for the detection of dopamine (DA) in the presence of ascorbic acid (AA). The structure and morphology of the obtained MG were analyzed by X‐ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy, high‐resolution transmission electron microscopy, and nitrogen adsorption–desorption isotherms. The obtained MG was dispersed in DMF solution and then drop‐casted on to a platinum plate. It was primarily tested for electrochemical sensing of biomolecules. Cyclic voltammetry and differential pulse voltammetry (DPV) were used to evaluate the electrochemical behaviors of MG on a platinum electrode. DPV facilitated selective and sensitive detection of DA in the presence of a high concentration of AA. MG showed a faster electron transfer rate and increased current density. It exhibited good sensitivity, selectivity, and a linear relationship with concentration, with a 7 μM limit of detection, suggesting that MG is a promising material for electrochemical sensing applications.