Worldwide legislation coming into force requires considering new waste streams in order to achieve higher targets for material recovery and recycling. It is necessary, therefore, to manage waste materials in which different components are linked together and contaminants of various origins are present. Waste materials thus need to be treated that have a complex and often unknown composition and present different structural, morphological, and chemical properties. The physical and chemical characterization of solid waste is an essential step for the development of suitable treatment strategies, aimed at the recovery of one or more waste components. Scanning electron microscopy appears to be in most cases very helpful for waste characterization, providing information on material size, shape, structure, texture, distribution, and composition. Examples of waste characterization through scanning electron microscopy, finalized to material recovery, are reported. The waste materials taken into consideration include solids of different nature, such as spent lead batteries, cathode ray tubes (CRT), and printed circuit boards (PCB).