Graphite is used increasingly as cathode for aluminium electrolysis cell, which shows a better electrical conductivity and less energy loss in the process. Liquid aluminum does not wet graphite, and react with graphite to form aluminium carbide (Al4C3), which is the cause that limits the lifespan of cathodes. The TiB2 coating of wettable cathodes has the potential to give enormous benefits to the aluminum electrolysis industry in terms of energy cost saving and prolonged cell life. Plasma spraying is a cost-effective and highly flexible method for depositing coatings including intermetallics, ceramics and composites with a thickness from several micrometers to millimeters on substrates of complicated shapes and with a large area. Plasma Sprayed TiB2 coating of wettable cathodes is a known technique. This review covers the development of plasma sprayed TiB2 coatings of wettable cathodes for aluminum electrolysis. This article outlined the influencing factors of plasma spraying (including the powder properties, the surface morphology of substrate material and the flame flow properties), and the binding mechanism between coatings materials and substrate materials (including mechanical bonding, metallurgical bonding and physical bonding). The TiB2 powder preparation, pretreatment of carbon blocks and plasma spraying process were reviewed, and then the microstructure and properties of plasma spraying TiB2 coatings were discussed. At the end, some key problems in the future researches of plasma spraying TiB2 coating of wettable cathodes were also outlined.