This study investigated the fast pyrolysis behaviour of torrefied olive stones, fractionated olive stones and lignocellulosic commercial compounds. Olive stones were reacted in a continuous industrial torrefaction unit. The olive stones were also fractionated into their main components in an organosolv reactor at temperatures from 170 to 190 °C in both the presence and absence of an acidic catalyst. All samples were reacted in a wire mesh reactor at different temperatures (800–1150 °C) and heating rates (400–1150 °C/s), and the solid product was characterised for its yield, morphology, and elemental composition. The char yields from fast pyrolysis of commercially available cellulose, hemicelluloses, and lignin were compared with yields of fractionated olive stones. A model was developed to compare the measured yields of olive stones with the predicted yields using fractionated or commercial components. The presence of acid during fractionation had a stronger effect than the temperature, particularly on the lignin fraction. The fractionated lignocellulosic compounds provided more accurate predictions of the char yields of olive stones, as compared to the commercial lignocellulosic compounds. The fractionation at 180 °C without acid catalyst gave the cellulose, hemicellulose, and lignin with highest degree of purity and resulted in the most accurate predictions of the experimental yields of olive stones. The results showed that interactions between the lignocellulosic components were not significant. The char yield of each fractioned compound and non-treated olive stones could be accurately predicted from the lignocellulosic content which has importance for biorefinery applications in which each fraction is used as a value-added product.