3D printing has been reported as a remarkable technology for development of electrochemical devices, due to no design constraints, waste minimization and, most importantly, fast prototyping. The use of 3D printed electrodes for electroanalytical applications is still a challenge and demand efforts. In this work, we have developed low-cost and reproducible 3D-printed graphene electrodes for electrocatalytic detection of dopamine. Electrocatalytic features were enhanced after electrochemical pre-treatment. The oxidation and reduction at different potential ranges, in 0.1 mol L−1 phosphate buffer solution (pH = 7.4), are used to modulate the structural and morphological characteristics of the electrodes. Since, the electrochemical properties of the electrodes, including electron transfer kinetic and the electrocatalytic activity, are strongly influenced by electronic properties and the presence of functional groups. Raman spectroscopy, SEM and AFM microscopes and electrochemical techniques were used to characterize the 3D electrodes before and after the electrochemical pre-treatments. Finally, the performances of the 3D-printed graphene electrodes were evaluated towards dopamine sensing. The best performance was achieved by oxidation at + 1.8 V vs. SCE for 900 s and reduction from 0.0 V to -1.8 V vs. SCE at 50 mV s−1. The proposed sensor presented linear response from 2.0 μmol L−1 to 10.0 μmol L−1, with detection limit of 0.24 μmol L−1.