Microbial electrolysis cells (MECs) are an electricity-mediated microbial bioelectrochemical technology, which is originally developed for high-efficiency biological hydrogen production from waste streams. Compared to traditional biological technologies, MECs can overcome thermodynamic limitations and achieve high-yield hydrogen production from wide range of organic matters at relatively mild conditions. This approach greatly reduces the electric energy cost for hydrogen production in contrast to direct water electrolysis. In addition to hydrogen production, MECs may also support several energetically unfavorable biological/chemical reactions. This unique advantage of MECs has led to several alternative applications such as chemicals synthesis, recalcitrant pollutants removal, resources recovery, bioelectrochemical research platform and biosensors, which have greatly broaden the application scopes of MECs. MECs are becoming a versatile platform technology and offer a new solution for emerging environmental issues related to waste streams treatment and energy and resource recovery. Different from previous reviews that mainly focus on hydrogen production, this paper provides an up-to-date review of all the new applications of MECs and their resulting performance, current challenges and prospects of future.