Microbial electrosynthesis (MES) is a novel microbial electrochemical technology proposed for chemicals production with the storage of sustainable energy. However, the practical application of MES is currently restricted by the limited low market value of products in one-step conversion process, mostly acetate. A theme that is pervasive throughout this review is the challenges associated with the expanded product spectrum. Several recent research efforts to improve acetate production, using novel reactor configuration, renewable power supply, and various 3-D cathode are summarized. The importance of genetic modification, two-step hybrid process, as well as input substrates other than CO2 are highlighted in this review as the future research paths for higher value chemicals production. At last, how to integrate MES with existing biochemicals processes is proposed. Definitely, more studies are encouraged to evaluate the overall performances and economic efficiency of these integrated process designs to make MES more competitive.