Generation of green electricity using innovative renewable and alternative energy technologies has shown merits and received renewed interest in recent years due to an increasing concern of greenhouse gas (GHG) emissions, being responsible for global warming & climate change, environmental pollution, and the limitations and conservation of natural energy resources. Thermoelectric power generation has emerged as a promising renewable and alternative green technology due to its distinct advantages. It offers a potential application in the direct conversion of waste-heat energy produced from automotive exhaust into electrical power where it is unnecessary to consider the cost of the thermal energy input. The application of this alternative green technology in converting waste-heat energy directly into electrical power can also improve the overall efficiencies of energy conversion systems. In this paper, the fundamental concept, composition and specifications, performance aspects, and innovative materials of thermoelectric power generation are presented. Also, recent developments and novel patents of thermoelectric power generation with their important and relevant applications to automotive exhaust waste-heat energy are reviewed and discussed.