Biowaste fermentation is a promising technology for low‐carbon print bioenergy and biochemical production. Although it is believed that the microbiome determines both the fermentation efficiency and the product profiles of biowastes, the explicit mechanisms of how microbial activity controls fermentation processes remained to be unexplored. The current study investigated the microbiome dynamics and fermentation product profiles of biowaste fermentation under different organic loads (5, 20, and 40 g‐VS/L) and with additives that potentially modulate the fermentation process via methanogenesis inhibition (2‐bromoethanesulfonate) or electron transfer promotion (i.e., reduced iron, magnetite iron, and activated carbon). The overall fermentation products yields were 440, 373 and 208 CH4‐eq/g‐VS for low‐, medium‐ and high‐load fermentation. For low‐ and medium‐load fermentation, volatile fatty acids (VFAs) were first accumulated and were gradually converted to methane. For high‐load fermentation, VFAs were the main fermentation products during the entire fermentation period, accounting for 62% of all products. 16S rRNA‐based analyses showed that both 2‐bromoethanesulfonate addition and increase of organic loads inhibited the activity of methanogens and promoted the activity of distinct VFA‐producing bacterial microbiomes. Moreover, the addition of activated carbon promoted the activity of H2‐producing Bacteroides, homoacetogenic Eubacteriaceae and methanogenic Methanosarcinaceae, whose activity dynamics during the fermentation led to changes in acetate and methane production. The current results unveiled mechanisms of microbiome activity dynamics shaping the biowaste fermentation product profiles and provided the fundamental basis for the development of microbiome‐guided engineering approaches to modulate biowaste fermentation toward high‐value product recovery.