The incorporation and effective anchorage of gold nanorods in a gold (111) is applied to electrochemical detection of dopamine. Gold nanorods (AuNRs) were synthesized in dispersion and incorporated in a metal substrate mediated by self-assembled monolayers (SAMs) which act as structural anchors. Two molecular anchors, 4-mercaptobenzoic acid (4-MBA) and 4 aminothiophenol (4-ATP), are compared by charge density (Q) in desorption of the SAMs, where 4-MBA presented a greater coverage on the metal surface. Both SAMs allowed the effective confinement and communication of nanostructure to a greater or lesser extent. Characterizations were made to confirm the constructed system. First, the nanostructures synthesized in dispersion were characterized by UV-visible, transmission electron microscopy, and atomic force microscopy. Then, an electrochemical characterization of the working electrodes include impedance was made. The results focus on the molecular anchor on the activity of electrochemical sensor. Reducing the charge transfer resistance (by at least 90%) of molecularly anchored gold nanorods increases the sensitivity of the electrochemical sensor (at least 20%), the detection of dopamine was studied through a calibration curve, where better sensitivity and detection limit was obtained with the Au/4-MBA/AuNRs system compared to Au/4-ATP/AuNRs.