This article presents a methodology for determining the kinetic parameters of biomass based on thermogravimetric analysis and the Coats–Redfern procedure with 27 model equations. Maize samples stored for approximately one year were used herein. The first sub-stage of pyrolysis was a first-order reaction with nuclei growth of n = 1, and the second sub-stage indicated a different kinetic order (1.5) of the reaction. The last sub-step showed good convergence with the first-order reaction and nuclei growth of n = 1.5. The activation energy reached up to 71.6 kJ/mol for tżhe selected parts of the stalk fraction, whereas it decreased to 6.5 kJ/mol for the others. A simplified method for approximating the composition of the biomass is also presented. In the composition of stalks, the fraction of hemicellulose was the highest, followed by that of cellulose, whereas in the composition of leaves and whole plant samples, an opposite trend was observed.