A new system for the microscopic classification of fly-ash components has been developed by the Fly-Ash Working Group, Commission III of the ICCP and is presented herein. The studied fly-ashes were obtained from the combustion of single coals of varied rank, coal blends, and coals blended with other fuels (biomass, petroleum coke), in different operating conditions and by means of different technologies. Microscopic images of the fly-ash samples were used to test the optical criteria proposed for classifying the fly-ash components. The classification system developed is based on a small number of microscopic criteria, subdivided into six independent levels or categories, three of which are directed at whole particle identification on the basis of nature, origin and type of fly-ash particle, while the other three levels are directed at the smaller section identification on the basis of character, structure and optical texture of unburned carbons. To classify the inorganic components of the fly-ash, the criterion proposed is composition in terms of metallic/non-metallic character. To establish the classification criteria the petrographers involved in the work performed three successive round robins. Evaluation of the results by using firstly descriptive statistics and then the criteria and parameters employed by the ICCP in their accreditation programs indicated that the classification of the fly-ash components was accurate and that there was only a minor bias. The main conclusion of this study was that the proposed criteria are valuable for identifying, and classifying fly-ash components and for describing the optical properties of fly ash particles.