Over the last years, graphene is deemed as one of the most promising electrode materials for EDLCs due to its large specific surface area (2600 m2·g-1), high theoretical specific capacitance (550 F·g-1) and high conductivity1. Among all the reported approaches to achieve a graphene-like material, the most favorable route is the reduction of GO and notably the electrochemical reduction of GO that is viewed as an economic, simple, fast and eco-friendly method with production possibility at a relatively large scale2-3. However, reduced graphene oxide (rGO) suffers from the small surface area due to the partial re-stacking of graphene sheets through π−π interactions4. Therefore, it is necessary to develop an effective and feasible route to avoid rGO re-stacking to obtain graphene-based electrodes with a high specific capacitance and a good stability. Herein, we report graphene-PDA composites as electrodes for micro-supercapacitor devices fabricated by a facile electrochemical approach5. We particularly address the rGO re-stacking issue by exploiting the PDA as a “chemical insert” between the graphene sheets but also explore the impact of PDA on the interfacial charge storage properties and the cycling performance. The optimized ERGO-PDA electrode possesses combined features of excellent capacitive behavior: high gravimetric and volumetric capacitances (178 F·g-1 and 297 F·cm- 3, respectively, at 10 mV·s-1) with an excellent cycling stability (Figure 1: 107 % of capacitance retention after 10000 cycles at a scan rate of 1000 mV·s-1). Additionally, the electrochemical quartz crystal microbalance analyses demonstrate a dominant cationic charge compensation and a very efficient interfacial transfer characteristics in the presence of PDA, since a totally reversible mass response during charge/discharge was observed for the optimized ERGO-PDA electrode. Here the favourable impact of PDA is shown to tackle rGO restacking issue, shedding light on the design of graphene based composite electrodes and can also be extended to other 2D materials for high performance electrochemical energy storage electrodes. References (1) Tan, Y. B.; Lee, J.-M. Journal of Materials Chemistry A 2013, 1 (47), 14814-14843 (2) Gao, W.; Debiemme-Chouvy, C.; Lahcini, M.; Perrot, H.; Sel, O. Analytical Chemistry 2019, 91 (4), 2885-2893. (3) Guo, H.-L.; Wang, X.-F.; Qian, Q.-Y.; Wang, F.-B.; Xia, X.-H. ACS Nano 2009, 3 (9), 2653-2659 (4) Banda, H.; Périé, S.; Daffos, B.; Taberna, P.-L.; Dubois, L.; Crosnier, O.; Simon, P.; Lee, D.; De Paëpe, G.; Duclairoir, F., ACS Nano 2019, 13 (2), 1443-1453 (5) Bouzina, A.; Perrot, H.; Sel, O.; Debiemme-Chouvy, C. ACS Applied Nano Materials 2021, 4 (5), 4964–4973