Volatile fatty acids (VFAs) production plays an important role in the process of anaerobic digestion (AD), which is often the critical factor determining the metabolic pathways and energy recovery efficiency. Fermenting bacteria and acetogenic bacteria are in syntrophic relations during AD. Thus, clear elucidation of the interspecies electron transfer and energetic mechanisms among syntrophic bacteria is essential for optimization of acidogenic. This review aims to discuss the electron transfer and energetic mechanism in syntrophic processes between fermenting bacteria and acetogenic bacteria during VFAs production. Homoacetogenesis also plays a role in the syntrophic system by converting H2 and CO2 to acetate. Potential applications of these syntrophic activities in bioelectrochemical system and value-added product recovery from AD of organic wastes are also discussed. The study of acidogenic syntrophic relations is in its early stages, and additional investigation is required to better understand the mechanism of syntrophic relations.