Thermophiles are promising options to use as electrocatalysts for bioelectrochemical applications including microbial electrolysis. They possess several interesting characteristics such as ability to catalyze a broad range of substrates at better rates and over a broad range of operating conditions, and better electrocatalysis/electrogenic activity over mesophiles. However, a very limited number of investigations have been carried out to explore the microbial reactions/pathways and the molecular mechanisms that contribute to better electrocatalysis/electrolysis in thermophiles. Here, we review the electroactive characteristics of thermophiles, their electron transfer mechanisms, and molecular insights behind the choice of thermophiles for bioelectrochemical/electrolytic processes.