Fuel cell reactors can be tailored to simultaneously cogenerate value-added chemicals and electrical energy while releasing negligible CO₂ emissions or other pollution; moreover, some of these reactors can even "breathe in" poisonous gas as feedstock. Such clean cogeneration favorably offsets the fast depletion of fossil fuel resources and eases growing environmental concerns. These unique reactors inherit advantages from fuel cells:a high energy conversion efficiency and high selectivity. Compared with similar energy conversion devices with sandwich structures, fuel cell reactors have successfully "hit three birds with one stone" by generating power, producing chemicals, and maintaining eco-friendliness. In this review, we provide a systematic summary on the state of the art regarding fuel cell reactors and key components, as well as the typical cogeneration reactions accomplished in these reactors. Most strategies fall short in reaching a win-win situation that meets production demand while concurrently addressing environmental issues. The use of fuel cells (FCs) as reactors to simultaneously produce value-added chemicals and electrical power without environmental pollution has emerged as a promising direction. The FC reactor has been well recognized due to its "one stone hitting three birds" merit, namely, efficient chemical production, electrical power generation, and environmental friendliness. Fuel cell reactors for cogeneration provide multidisciplinary perspectives on clean chemical production, effective energy utilization, and even pollutant treatment, with far-reaching implications for the wider scientific community and society. The scope of this review focuses on unique reactors that can convert low-value reactants and/or industrial wastes to value-added chemicals while simultaneously cogenerating electrical power in an environmentally friendly manner.