AbstractBiomass pyrolysis process from a drop tube reactor was modelled in a plug flow reactor using Aspen Plus process simulation software. A kinetic mechanism for pyrolysis was developed considering the recent improvements and updated kinetic schemes to account for different content of cellulose, hemicellulose, and lignin. In this regard, oak, beechwood, rice straw, and cassava stalk biomasses were analyzed. The main phenomena governing the pyrolysis process are identified in terms of the characteristic times. Pyrolysis process was found to be reaction rate controlled. Effects of pyrolysis temperature on bio‐oil, gases, and char yields were evaluated. At optimum pyrolysis conditions (i.e., 500°C), a bio‐oil yield of 67.3, 64, 43, and 52 wt.% were obtained from oak, beechwood, rice straw, and cassava stalk, respectively. Oak and beechwood were found to give high yields of bio‐oil, while rice straw produced high gas and char yields compared to other biomasses. Although temperature is the main factor that plays a key role in the distribution of pyrolysis products, the composition of cellulose, hemicellulose, and lignin in the feedstock also determines the yield behaviour and composition of products. With the rise in pyrolysis temperature, further decomposition of intermediate components was initiated favouring the formation of lighter fractions. Comparably, species belonging to the aldehyde chemical family had the highest share of bio‐oil components in all the investigated feedstocks. Overall, the present study shows a good agreement with the experimental study reported in the literature, confirming its validity as a predictive tool for the biomass pyrolysis process.