Fifteen standard coal samples from the European Centre for Coal Specimens (SBN) were analyzed by pyrolysis-gas chromatography equipped with a flame ionization detector and a name photometric detector (PST-GC(FID/FPD)). The yields of sulfur obtained when coal samples were pyrolyzed and combusted were between 56 and 80% of the total amount of sulfur present. The total amount of sulfur in the pyrolysis products was proportional to the sulfur content of the coals. The data obtained were evaluated with principal component analysis (PCA) and partial least-squares (PLS) regression. Predictive models for the content of total sulfur, organic sulfur, pyritic sulfur, and inorganic sulfur (the sum of pyritic and sulfate sulfur) were built. It was also possible to obtain a predictive model for the content of volatile matter.