Due to the fact that much of the world's best solar resources are inversely correlated with population centers, significant motivation exists for developing technology which can deliver reliable and autonomous conversion of sunlight into electricity. Thermoelectric generators are gaining incremental ground in this area since they do not require moving parts and work well in remote locations. Thermoelectric materials have been extensively used in space satellites, automobiles, and, more recently, in solar thermal applications as power generators, known as solar thermoelectric generators (STEG). STEG systems are gaining significant interest in both concentrated and non-concentrated systems and have been employed in hybrid configurations with solar thermal and photovoltaic systems. In this article, the key developments in the field of thermoelectric materials and on-going research work on STEG design conducted by various researchers to date are critically reviewed. Finally, we highlight the strategic research directions being undertaken to make highly efficient thermoelectric materials for developing a cost-effective STEG system, which could serve to bring this technology towards commercial readiness. This journal is © the Partner Organisations 2014.