Biomass-derived humins produced in the biorefining of biomass represent an attractive feedstock for thermochemical processes and other carbon-derived platform chemicals. However, in most works, humins are merely a by-product that is not further analyzed. This work presents the purification and characterization of humins derived from sugarcane bagasse and rice husks (H-SCB and H-RH respectively), followed by the kinetic and thermodynamic analysis of its pyrolysis. Pyrolysis was examined via thermogravimetric analysis (TGA), and a global reaction model was adopted to address pyrolysis kinetics. To understand the pyrolysis process of humins and boost the quality of fit between the kinetic model and thermoanalytical data, the analyses were based on the Vyazovkin isoconversional method. The activation energy of H-SCB increased from 166.09 to 329.76 kJ mol-1. In contrast, the activation energy of H-RH decreased from 163.31 to 84.99 kJ mol-1. According to the results of the generalized master plot approach, the governing reaction mechanism shifted among order-based models, nucleation, and diffusion-controlled particle mechanisms. Derived thermodynamic properties showed that the heat absorbed helps the humins to achieve a more ordered state close to a conversion of 0.50. As far as we know, these findings are the first reported data on the forecast kinetic curves and pyrolysis mechanism of biorefinery-derived humins from sugarcane bagasse and rice husk, and these results will enable process design for the thermochemical conversion of these emerging materials to produce energy and other products.