The first study in the literature on the pyrolysis of pequi (Caryocar brasiliense) residues, focusing on the kinetic triplet, thermodynamic parameters, and characterization of volatile products utilizing TGA and Py−GC/MS techniques, is presented in this paper. Slow pyrolysis experiments were conducted on a thermogravimetric scale in a controlled atmosphere of pure nitrogen, with five distinct heating rates (5, 10, 20, 30 and 40 ºC min−1). The pyrolysis progress profiles were fitted using the Asym2Sig function to deconvolute the devolatilization rates of individual biomass pseudo-components, including extractives, hemicellulose, cellulose, and lignin. The average activation energies for pequi peel pyrolysis, as determined by the isoconversional methods of Friedman, Flynn−Wall−Ozawa, Kissinger−Akahira−Sunose and Starink, were higher (114.30 −319.13 kJ mol−1) than those estimated for pequi seeds (88.05 −168.39 kJ mol−1). The pre-exponential factors, obtained through the kinetic compensation effect method, exhibited a range of values between 3.6 × 1011 and 2.4 × 1030 min−1 for pequi peel and between 1.2 × 107 and 9.4 × 108 min−1 for pequi seeds. Utilizing the master-plots method revealed the involvement of F-type, A-type, and D-type reaction models in the pyrolysis of pequi residues. A slight difference between the Ea and ΔH values, less than 5 kJ mol−1, indicates the facile formation of reaction products during pyrolysis. The main organic volatile products obtained from the fast pyrolysis of pequi peel, as revealed by Py−GC/MS analysis, include furans, ketones, aldehydes, and ethers, constituting up to 52% of the total yield of the condensable fraction at 550 °C. Aliphatic hydrocarbons are the major organic volatile products derived from the fast pyrolysis of pequi seeds, accounting for approximately 74% of the total condensable fraction yield at 650 °C. This study provides new insights into the valorization of residues resulting from pequi fruit processing. As a result, a novel pathway for bioenergy and biobased chemical production via pyrolysis is established, aligning with the circular economy principle and capable of promoting energy matrix diversification.