A suite of tuyere-level coke samples have been withdrawn from a working blast furnace during coal injection, using the core-drilling technique. The samples have been characterized by size exclusion chromatography (SEC), Fourier transform Raman spectroscopy (FT-RS), and X-ray powder diffraction (XRD) spectroscopy. The 1-methyl-2-pyrrolidinone (NMP) extracts of the cokes sampled from the “bosh”, the rear of the “birdʼs nest”, and the “dead man” zones were found by SEC to contain heavy soot-like materials (ca. 107–108 apparent mass units). In contrast, NMP extracts of cokes taken from the raceway and the front of the “birdʼs nest” only contained a small amount of material of relatively lower apparent molecular mass (up to ca. 105 u). Since the feed coke contained no materials extractable by the present method, the soot-like materials are thought to have formed during the reactions of volatile matter released from the injectant coal, probably via dehydrogenation and repolymerization of the tars. The Raman spe...