Here we propose copper as a high performance and economically viable anode material for microbial bioelectrochemical systems.

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Here, we propose the use of in situ autofluorescence spectroelectrochemistry to gain access to the mechanisms of the extracellular electron transfer (EET) of electrochemically active bacteria. By studying the spectroelectrochemical behavior of biofilms enriched with Geobacter anodireducens, we i) determine the chemical nature of the respective EET components, ii) address kinetic EET aspects, and iii) propose potential‐dependent structural changes of outer membrane cytochromes during EET.