Lead-rich solid industrial wastes were vitrified by the addition of glass formers in various concentrations, to produce non-toxic vitreous stabilized products that can be freely disposed or used as construction materials. Toxicity of both the as-received industrial solid waste and the stabilized products was determined using standard leaching test procedures. The chemically stable vitreous products were subjected to thermal annealing in order to investigate the extent of crystal separation that could occur during cooling of large pieces of glass. Leaching tests were repeated to investigate the relation between annealing process and chemical stability. X-ray, scanning and transmission electron microscopy techniques were employed to identify the microstructure of stabilized products before and after thermal treatment. Relation between synthesis and processing, chemical stability and microstructure was investigated.