Various new energy technologies have been developed to reduce reliance on fossil fuels. The bioelectrochemical system (BES), an integrated microbial-electrochemical energy conversion process, is projected to be a sustainable and environmentally friendly energy technology. However, low power density is still one of the main limiting factors restricting the practical application of BESs. To enhance power output, functional group modification on anode surfaces has been primarily developed to improve the bioelectrochemical performances of BESs in terms of startup, power density, chemical oxygen demand (COD) removal and coulombic efficiency (CE). This modification could change the anode surface characteristics: roughness, hydrophobicity, biocompatibility, chemical bonding and electrochemically active surface area. This will facilitate bacterial adhesion, biofilm formation and extracellular electron transfer (EET). Additionally, some antibacterial functional groups are applied on air cathodes in order to suppress aerobic biofilms and enhance cathodic oxygen reduction reactions (ORRs). Various modification strategies such as: soaking, heat treatment and plasma modification have been reported to introduce functional groups typically as O-, N- and S-containing groups. In this review, the effects of anode functional groups on electroactive bacteria through the whole biofilm formation process are summarized. In addition, the application of those modification technologies to improve bioelectricity generation, resource recovery, bioelectrochemical analysis and the production of value-added chemicals and biofuels is also discussed. Accordingly, this review aims to help scientists select the most appropriate functional groups and up-to-date methods to improve biofilm formation.