Kinetic triplet, thermal degradation behaviour and thermodynamic properties of peanut shells were determined on the basis of non-isothermal thermogravimetric experiments conducted at three different heating rates under N2 atmosphere. A single differential peak was observed for the devolatilization stage. The kinetic triplet of devolatilization stage was determined using Coats-Redfern and a combined method consisting the utilization of isoconversional and Criado methods. Kinetic validation revealed that the kinetic triplet determined using the combined method described the experimental values more precisely. The reaction mechanism ascertained by the combined method was D5-D3 combination. The Ea value was strong function of conversion, and computed using isoconversional methods (Boswell, Flynn-Wall-Ozawa, Starink, Tang) between 169 and 268 kJ/mol. Entalphy, entrophy and Gibbs energy changes were computed in 164–259 kJ/mol, −37–141 J/(mol.K) and 173–187 kJ/mol ranges, respectively. The comprehensive pyrolysis index values were also calculated, and shown to increase with increasing heating rate.