On account of the continuous decrease in oil reserves, as well as the promotion of sustainable policies, there is an increasing interest in biomass conversion processes, which imply the search for new raw materials as energy sources, like forestry and agricultural wastes. On the other hand, gasification seems to be a suitable thermal conversion process for this purpose. This work studied the thermogravimetry of the steam gasification of charcoal from heather (Calluna vulgaris) in order to determine the kinetics of the process under controlled reaction conditions. The variables studied were temperature (from 750 to 900 °C), steam partial pressure (from 0.26 to 0.82 atm), initial charcoal mass (from 50 to 106 mg), particle size (from 0.4 to 2.0 mm), N2 and steam volumetric flows (from 142 to 446 mL·min−1) and catalyst (K2CO3) concentration (from 0 to 10% w/w). The use of the shrinking core model and uniform conversion model allowed us to determine the kinetic parameters of the process. As a result, a positive influence of catalyst concentration was found up to 7.5% w/w. The kinetic study of the catalytic steam gasification showed activation energies of 99.5 and 114.8 kJ·mol−1 and order of reactions (for steam) of 1/2 and 2/3.