Coal combustion in power plants for electric power generation produces millions of tons of residues that are generally disposed of in landfills or ponds occupying vast land, resulting in serious environmental pollution. Fly ash (FA) is one of the main solid wastes generated in coal-based thermal power plants, representing the largest fraction of coal combustion residues (65–95%). Unfortunately, the enormous amount of FA residue is utilized only partly, mainly in the cement industry and building materials field. An alternative approach to using FA is its incorporation into ceramic, glass and glass–ceramic production, aligning with circular economy principles and reducing the environmental footprint of both the energy and ceramic sectors. In this review article, the topics of the composition, properties, classification, and utilization of fly ashes from thermal power plants are discussed. The main objective of this work is a critical analysis of the experimental trials directed to the involvement of FA as a raw material in the fabrication of glass–ceramics and porous ceramic composites.