Abstract The influence of biomass macromolecular composition on its behaviour in torrefaction was statistically assessed through Principal Component Analysis (PCA), both in terms of solid conversion kinetics and volatile species released, in function of the operating conditions. The experimental data obtained in the torrefaction of 14 woody and agricultural biomass samples at lab-scale was analysed. Main biomass macromolecular composition on cellulose, hemicelluloses and lignin was shown to acceptably represent biomass diversity, which can be complemented by the extractives and ash content. Similitudes were found in deciduous and coniferous wood families, respectively, while agricultural and herbaceous crops were shown as more heterogeneous, both in terms of characterization and behaviour in torrefaction. Cellulose, hemicelluloses and lignin content strongly influenced solid and volatile species yields in torrefaction, while biomass family exhibited a lower impact. Ash content in potassium, phosphorous and silicon did not show any influence on the extent of solid degradation through torrefaction. A lower variability was found in solid degradation profiles from woods, while agricultural crop behaviour was more heterogeneous. Different volatile species were released from biomass samples from the same family. Furthermore, different production profiles were found for volatile species chemically close, except for deciduous wood. These results indicate that, when modelling biomass torrefaction, solid mass loss can be represented by an exemplar of deciduous and coniferous wood, while several species would be required for the agricultural family. The variability of the volatile species release would require the consideration of several volatile species and several biomass samples per family.