Olive trimmings (OT) were used as feedstock for an in-depth experimental study on the reaction kinetics controlling hydrothermal carbonization (HTC). OT were hydrothermally carbonized for a residence time τ of up to 8 h at temperatures between 180 and 250 °C to systematically investigate the chemical and energy properties changes of hydrochars during HTC. Additional experiments at 120 and 150 °C at τ = 0 h were carried out to analyze the heat-up transient phase required to reach the HTC set-point temperature. Furthermore, an original HTC reaction kinetics model was developed. The HTC reaction pathway was described through a lumped model, in which biomass is converted into solid (distinguished between primary and secondary char), liquid, and gaseous products. The kinetics model, written in MATLABTM, was used in best fitting routines with HTC experimental data obtained using OT and two other agro-wastes previously tested: grape marc and Opuntia Ficus Indica. The HTC kinetics model effectively predicts carbon distribution among HTC products versus time with the thermal transient phase included; it represents an effective tool for R&D in the HTC field. Importantly, both modeling and experimental data suggest that already during the heat-up phase, biomass greatly carbonizes, in particular at the highest temperature tested of 250 °C.