To achieve energy transition, hydrogen and carboxylic acids have attracted much attention due to their cleanliness and renewability. Anaerobic fermentation technology is an effective combination of waste biomass resource utilization and renewable energy development. Therefore, the utilization of anaerobic fermentation technology is expected to achieve efficient co-production of hydrogen and carboxylic acids. However, this process is fundamentally affected by gas–liquid mass transfer kinetics, bubble behaviors, and system partial pressure. Moreover, the related studies are few and unfocused, and no systematic research has been developed yet. This review systematically summarizes and discusses the basic mathematical models used for gas–liquid mass transfer kinetics, the relationship between gas solubility and mass transfer, and the liquid-phase product composition. The review analyzes the roles of the headspace gas composition and partial pressure of the reaction system in regulating co-production. Additionally, we discuss strategies to optimize the metabolic pathways by modulating the gas composition and partial pressure. Finally, the feasibility of and prospects for the realization of hydrogen and carboxylic acid co-production in anaerobic fermentation systems are outlined. By exploring information related to gas mass transfer and system pressure, this review will surely provide an important reference for promoting cleaner production of sustainable energy.