The pyrolysis of four pairs of raw and acid-washed coals under N2 atmosphere was carried out in a drop tube reactor at 1250 °C. The results show that both organic structures and metal elements have an important influence on the formation of soot. The total area of aromatic and aliphatic hydrogen absorption bands is positively correlated with soot yield. Aromatic compounds have a greater contribution to soot and tar formation. The absorption band area of oxygen structures in coal FTIR spectra is negatively correlated with the soot conversion rate of tar. During pyrolysis, metal substances in coal can catalyze the dehydrogenation and deoxygenation of tar, reduce the content and stability of the aliphatic compound, and catalyze aromatic ring rupturing. More importantly, gasified metals can inhibit the polymerization reaction of aromatic compounds.