The unconsumed pulverized coal and coke in flue dusts from two blast furances (BFs) were investigated in this paper. The percentage of unconsumed pulverized coal and coke were determined by means of chemical and petrographical microanalyses, which were time-consuming, requiring special expertise, and cannot be practiced routinely. Therefore, a simplified quantification method was proposed. The percentage of these materials in the BF flue dust samples was established on the basis of a suitable calibration using char and coke standards by Raman spectroscopy. The ratios of I-D/I-G, I-V/I-G, and I-2D/I-G were used to estimate constitutents of the BF flue dust. The amount of unconsumed pulverized coal in 1BF and 2BF was 9.7 and 11.6%, respectively, by means of petrographical microanalysis, and that in 1BF and 2BF established by Raman spectroscopy was in the ranges of 810 and 10.512%, respectively. The results showed that Raman spectroscopy was a relatively rapid and effective monitoring technique for the purpose of differentitation between coke and uncomsumed pulverized coal in BF flue dust.