A series of activated carbons (YMBC) obtained from yerba mate twig residue (YMT) were prepared by chemical (H₃PO₄) and thermal activation. Five materials were synthesized, varying the carbonization temperature (400–600 °C under N₂ atmosphere) and H₃PO₄:YMT ratio (60–80 wt%). They were physicochemically and texturally characterized by SEM-EDX, BET, FT-IR, and ³¹P MAS-NMR. Potentiometric titration with the n-butylamine technique was used to evaluate their acidic properties. The materials exhibited a high specific surface area (572 m² g⁻¹ < S_BET < 1031 m² g⁻¹) and mesoporosity (67% < S_meso/S_BET < 93%). The results showed that the acid strength and the number of acid sites increased with the H₃PO₄:YMT ratio and decreased with the calcination temperature increment. The FT-IR and ³¹P characterization revealed the presence of H_n+2P_nO_3n+1 species firmly (via P-O-C linkages) and loosely attached (by electrostatic interaction). The latter were successfully removed by refluxing the material in water or n-propanol. The optimal reaction conditions were applied to the synthesis of other levulinic acid esters using YMBC-500-70_NP as a catalyst. Furthermore, the effective separation of the product combined with the use of a recyclable catalyst resulted in a clean and environmentally friendly strategy for the synthesis of alkyl levulinates, bioproducts of relevance to the biorefinery industry, which can be applied as fragrances, flavoring agents, as well as fuel additives.