Research Highlights: Biomass from Mediterranean agroforestry vegetation may be a potential source of renewable energy. However, due to the high heterogeneity of this type of resource, the study of its characteristics becomes necessary for its efficient use. Objectives: The aim of this study was to evaluate the thermal and chemical properties of 14 different kinds of agroforestry biomass groups: shrubs, forest, and agricultural wastes. Materials and Methods: The higher heating value (HHV), the elemental analysis (C, H, O, N, S), ashes, mineral elements (Na, K, Ca, Mg, and P), trace elements (Mn, Fe, Zn, Ni, Cu, Cr, and Cd) and halogen elements (F and Cl) were quantified and compared with CEN/TS 147775 and CENS/TS 14961 standards, looking forward to future use for energy purposes, namely through combustion processes, as an alternative to fossil fuels. Results: The shrubs present the highest values of higher heating value (20.5 MJ kg−1), followed by the forest wastes (19.2 MJ kg−1) and the lowest in the agricultural wastes (18.5 MJ kg−1). Concerning the elemental analysis, the difference between groups C, H, and O are very small and not statistically significant, while for N, S and ashes values are higher in agricultural than shrubs and forestry wastes. The same tendency was found for the mineral nutrients. For the trace elements, the lowest content of Mn, Fe, and Zn is found in agricultural, Ni, and Cr content in the shrubs and Cu in the forest wastes. The halogen elements are present in greater amount in shrubs than agricultural and forest wastes. Conclusions: Although the high values of the halogen elements which may raise sintering problems and corrosive effect on metal parts in furnace and boiler, in general the shrubs biomass are those with better characteristics for energy uses, namely through combustion processes.