This paper presents an extensive review of the scientific literature associated with various microwave pyrolysis applications in waste to energy engineering. It was established that microwave-heated pyrolysis processes offer a number of advantages over other processes that use traditional thermal heat sources. In particular, microwave-heated processes show a distinct advantage in providing rapid and energy-efficient heating compared to conventional technologies, and thus facilitating increased production rates. It can also be established that the pyrolysis process offers an exciting way to recover both the energetic and chemical value of the waste materials by generating potentially useful pyrolysis products suitable for future reuse. Furthermore, this review has revealed good performance of the microwave pyrolysis process when compared to other more conventional methods of operation, indicating that it shows exceptional promise as a means for energy recovery from waste materials. Nonetheless, it was revealed that many important characteristics of the microwave pyrolysis process have yet to be raised or fully investigated. In addition, limited information is available concerning the characteristics of the microwave pyrolysis of waste materials. It was thus concluded that more work is needed to extend existing understanding of these aspects in order to develop improvements to the process to transform it into a commercially viable route to recover energy from waste materials in an environmentally sustainable manner.