Abstract This chapter discusses solar cells made of III–V semiconductors, and how they have reached efficiencies of over 46% in 2016, the highest of any photovoltaic technology to date. These high efficiencies are possible due to the ability of stacking solar cells made of different III–V semiconductors. The main focus of current research is on III–V multijunction solar cells with three or more junctions. III–V Solar cells are widely used in space applications, terrestrial concentrators as well as niche markets such as power-by-light or thermophotovoltaics. Today III–V devices find terrestrial applications only under high concentration. But III–V on silicon may be an attractive path to reduce cost and eventually penetrate this high-performance technology into conventional applications of flat-plate photovoltaics.