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The recent energy crisis and environmental burden are becoming increasingly urgent and drawing enormous attention to solar-energy utilization. Direct solar thermal power generation technologies, such as thermoelectric, thermionic, magnetohydrodynamic, and alkali-metal thermoelectric methods, are among the most attractive ways to provide electric energy from solar heat. On the one hand, these methods have the potential to be more efficient than traditional ways since they can convert heat to electricity directly without experiencing the conventional intermediate mechanical energy conversion process; on the other hand, these electricity generators are generally silent, reliable, and scalable, making them very suitable to serve as a distributed power generation system for certain specialized fields, such as military and space applications. A lot of effort has been devoted to investigate the energy conversion theory and practical applications thus far. This paper is intended to present a thorough review on recent advances in developing the thermoelectric, thermionic, magnetohydrodynamic, and alkali-metal thermoelectric technologies for direct solar thermal power generation. Both the fundamental issues and latest application research are illustrated and critical issues are discussed. The paper concludes with a description of future developments expected in the subjects covered.