The work performed during this project allowed faster startup of Microbial Fuel Cells devices with reproducible power outputs. The work performed on cathodic reaction studies allowed the clarification of the different nitrogen species role at different pH solution as well as the scaffold metallic character contribution on the catalysis of interest by using both experimental and computational analyses. Following these results, the roles of graphitic nitrogen, pyridinic nitrogen and scaffold metallic character on the oxygen reduction reaction were then understood and we demonstrated that the influence of each of these variables is linked to the aqueous environment pH in which the catalyst is operating. The work performed on the anodic site linked the relation between surface hydrophilicity, saccharide structure and deposition protocol on the electroactive biofilm affinity. We studied the bioaffinity between two types of saccharides and exoelectrogenic biofilm and we developed an ecofriendly and non-expensive approach to reduce MFC startup delay of 30% with an increased reproducibility. Furthermore, HiBriCarbon project allowed the development of an antifoulant coverage that can be employed to prevent unwanted biofilm colonization and MFC components degradation. This approach is still based on non-expensive and non-toxic protocol as it is based on the same principle of the bio affine coatings with opposite result due to the different sugar chemistry. This will be beneficial for reducing MFC maintenance without further invasive techniques at unsustainable costs. HiBriCarbon project contributes to further understand the role of specific molecules on the electroactive biofilm affinity and it allowed the application of this protocol on a final working device. Furthermore, HiBriCarbon project allowed the production of performant, non toxic and economic non platinum based catalysts to produce energy at low costs. Both of the obtained achievements can be considered as next step for MFC commercialization in large scale. Furthermore, this will be beneficial to alternative renewable energy strategies that are becoming a priority due to climate change concerns: the studies performed in this work on anodic and cathodic reactions will help to decrease the existing reliance on fossil fuel-based electricity.