The study investigates the extracellular electron transfer (EET) pathways in *Geobacter sulfurreducens* using periplasmic cytochromes PpcABCDE to charge OmcS nanowires. Despite the crowded periplasm and slow electron diffusion among periplasmic cytochromes, the periplasmic cytochromes transiently bind to OmcS nanowires, injecting electrons directly into them. This pathway is evolutionarily conserved in diverse bacteria capable of EET and DIET. The reduction potential of OmcS nanowires is found to be 82 mV more positive than previously reported, eliminating the thermodynamic barrier for efficient EET. NMR spectroscopy reveals that PpcC, the least-abundant cytochrome, shows the highest electron transfer efficiency to OmcS nanowires. The study also demonstrates that the interaction between PpcA-E and OmcS is mediated by complementary surface charges and heme-to-heme proximity. This minimal nanowire-charging pathway is widespread in phylogenetically diverse bacteria, including thermophiles and those involved in bioremediation. The findings provide insights into how microbes rapidly transfer electrons over long distances, which is crucial for their survival in various environments.The study investigates the extracellular electron transfer (EET) pathways in *Geobacter sulfurreducens* using periplasmic cytochromes PpcABCDE to charge OmcS nanowires. Despite the crowded periplasm and slow electron diffusion among periplasmic cytochromes, the periplasmic cytochromes transiently bind to OmcS nanowires, injecting electrons directly into them. This pathway is evolutionarily conserved in diverse bacteria capable of EET and DIET. The reduction potential of OmcS nanowires is found to be 82 mV more positive than previously reported, eliminating the thermodynamic barrier for efficient EET. NMR spectroscopy reveals that PpcC, the least-abundant cytochrome, shows the highest electron transfer efficiency to OmcS nanowires. The study also demonstrates that the interaction between PpcA-E and OmcS is mediated by complementary surface charges and heme-to-heme proximity. This minimal nanowire-charging pathway is widespread in phylogenetically diverse bacteria, including thermophiles and those involved in bioremediation. The findings provide insights into how microbes rapidly transfer electrons over long distances, which is crucial for their survival in various environments.