Electron transfer is essential for the production efficiency of value-added products in anaerobic fermentation, such as butanol and ethanol as biofuels, and short-chain fatty acids (SCFAs) including butyric acid and acetic acid as platform chemicals. Electron mediators (EMs), also known as electron shuttles, can facilitate electron transfer to counter irreversible or slow redox reactions that limit fermentation. The addition of EMs has been shown to be an effective strategy to promote fermentation by various bacteria, particularly Clostridium species, for these valuable product syntheses. This paper reviews recent advancements in the application of exogenous electron mediators (EEMs) across various scenarios. Common EEM types, their characteristics, and mechanisms are summarized, and different application scenarios are discussed to elucidate the effect of EEMs. Key technical challenges and future directions for EEM application are also explored.