This paper will review the latest research and current status of thermoelectric power generation, and will also demonstrate, using electronic design, semiconductor simulation and practical laboratory experimentation, the application of thermoelectric technology for use in energy harvesting and scavenging systems. Ongoing research and advances in thermoelectric materials and manufacturing techniques, enables the technology to make a greater contribution to address the growing requirement for low-power energy sources typically used in energy harvesting and scavenging systems. The concept of using thermoelectric technology to generate electrical power from waste heat in a system has been considered for some time, although the technology is often overlooked in discussions surrounding renewable energy sources. This paper will discuss how the natural environment presents a number of opportunities to utilise this technology as a renewable energy source, including the use of thermoelectric technology to generate electrical power from naturally occurring geothermal heat. The paper covers basic thermoelectric theory, construction and operation of thermoelectric devices; the main advantages and disadvantages; and highlights several current and new applications for thermoelectric power generation. The application of this technology for use in energy harvesting systems is discussed, along with suitable electronic signal conditioning techniques; boost converters; DC to DC converters; and the storage of electrical energy in supercapacitors. This discussion then leads to the design, construction and testing of a thermoelectric energy harvesting system, with typical test results for thermoelectric power generation presented. The paper then focuses on current research into improving the power generation properties of thermoelectric modules, and a novel approach using semiconductor simulation techniques is presented. A novel three dimensional model of a thermoelectric device has been created using the Technology Computer Aided Design (TCAD) semiconductor simulation package, with typical simulation results for thermoelectric power generation presented