The fallen leaf has the potential to be energy-valorized in cities with sustainability goals. Thermochemical characterization of garden waste through pyrolysis and combustion kinetics will establish the reactivity of this lignocellulosic biomass as biofuel for thermochemical conversion processes for energy recovery. Herein, the thermal degradation of two types of pellets produced from fallen leaf (pellets without glycerol PG0, and pellets with 5 wt% glycerol PG5) are characterized under inert and oxidative atmospheres using three different approaches: thermogravimetry (TG) and differential thermogravimetry (DTG) analyses, TG-based reactivity, and reaction kinetics from three model-free isoconversional methods. The model-free isoconversional methods are Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Friedman, which were applied for estimating the kinetic parameters, activation energy (Eα) and pre-exponential factor, using different heating rates (20, 30, and 40 °C/min) to ensure reliable data interpretation. The pyrolysis results showed that PG5 was more reactive compared to PG0 because the addition of glycerol during the pelletizing process increased the volatile matter and oxygen content in PG5. Likewise, the higher reactivity of PG5 under pyrolysis was determined by average activation energy (Eα) with an average value of 96.82 kJ/mol compared to 106.46 kJ/mol for PG0. During the combustion process, Eα was 90.70 kJ/mol and 90.29 kJ/mol for PG0 and PG5, respectively. Finally, both materials exhibited higher reactivity under an oxidative atmosphere. Therefore, according to our results, the pellets produced from leaf litter can be used as biofuels for thermochemical processes, highlighting that using glycerol as a binder favors the reactivity of the densified garden waste.