Anaerobic digestion (AD) has been widely applied bioprocess to produce the biogas for fuels from organic waste degradation. AD has been integrated with other processes for increasing the digestion efficiency and waste valorization. The integration of AD with other bioprocess optimizes the production of targeted product and reduces the waste. Recently, microbial electrosynthesis (MES) was coupled with AD for the biomethane production, chemical synthesis and resource recovery. MES coupling to AD also gives an opportunity for value-added chemical generation and hence provides additional economic gains of integrated system. In MES, the remaining carbon dioxide (CO₂) in biogas is reduced to methane by methanogens utilizing in situ produced hydrogen at cathode, thereby enriching methane content. Furthermore, electroactive microbes could directly accept the electron from cathode to reduce the CO₂ to methane and chemicals. Therefore, CO₂ fraction in the biogas could be utilized for the further chemical synthesis such as acetate, butyrate. In this chapter, advances on AD technology and MES coupling with AD are thoroughly discussed for the production of fuels and chemicals. The outputs of recent laboratory scale experiments are summarized and discussed. Furthermore, mechanism of CO₂ reduction is elaborated with methane and chemical production.