Plastic waste poses a significant challenge in Africa and around the world, with its volume continuing to increase at an alarming rate. In Africa, an estimated 25–33% of daily waste is made up of plastic, posing a threat to the environment, marine life, and human health. One potential solution to this problem is waste-to-energy recycling, such as pyrolysis, which involves the conversion of waste materials into oil, char, and non-condensable gasses through a thermochemical process in the absence of oxygen. Given the abundance of waste in Africa and the continent’s energy challenges, pyrolysis offers a sustainable solution. This review delves into the concept of pyrolysis, its products, thermodynamics, and endothermic kinetics, presenting it as a promising way to address the plastic waste problem in Africa. Despite the African Union’s goal to recycle plastic waste, the continent faces significant barriers in achieving this target, including infrastructural, economic, and social difficulties. It is crucial to implement sustainable strategies for managing plastic waste in Africa to mitigate environmental degradation and promote a cleaner and healthier living environment. Pyrolysis technology is highlighted as a viable solution for plastic waste management, as it can convert plastic waste into valuable byproducts such as oil, char, and syngas. Case studies from countries like South Africa and Nigeria demonstrate the potential for scaling up pyrolysis to address waste management issues while generating energy and job opportunities. This review underscores the need for investment, regulatory support, and public awareness to overcome the challenges and unlock the full potential of pyrolysis in Africa. Embracing pyrolysis as a method for managing plastic waste could lead to significant environmental and economic benefits for the continent.