In this work, the petrology and chemistry of fly ashes produced in a Spanish power plant from the combustion of complex pulverized feed blends made up of anthracitic/meta-anthracitic coals, petroleum, and natural coke are investigated. Moreover, the original coals previous to blending as well as the feed blends were also characterized. The work is, thus, focused on the identification of the unburned carbon present in the resulting fly ashes after the combustion of these feed blends, on the establishment of a simple and comprehensive petrographic classification of the fly ash components, on the potential relationship between the amount and the type of fly ash carbons, and on their capacity for capturing Hg and Se as trace elements of environmental interest. It was found that the behavior of fly ash carbons derived from anthracitic coals follows relatively similar patterns to those established for the carbons from the combustion of bituminous coals. Fly ashes were sampled in eight hoppers from two electrostatic precipitator (ESP) rows. The characterization of the raw ashes and their five sieved fractions (from > 150 to < 25 mu m) showed that glassy material, quartz, oxides, and spinels in different proportions are the main inorganic components. As for the organic fraction, the dominant fly ash carbons are anisotropic carbons, mainly unburned carbons derived from anthracitic vitrinite. The concentration of Se and Hg increased in ashes of the second ESP row, this increase being related to the higher proportion of anisotropic unburned carbons, particularly those largely derived from anthracitic vitrinite in the cooler ashes of the ESP (second row) and also related to the decrease in the flue gas temperature. This suggests that the flue gas temperature plays a major role in the concentration of mercury for similar ratios of unburned carbons. It was also found that Hg is highly concentrated in the medium-coarser fractions of the fly ashes (> 45 mu m), there being a positive relationship between the amount of these carbons, which are apparently little modified during the combustion process, in the medium-coarse fractions of the ashes and the Hg retention. According to the results obtained, further research on this type of fly ash could be highly productive.