Coal fly ash (CFA) from different sources (CFA 5, 10, 13) and different size fractions (> or < 75 mu m) were characterized and used as inorganic supports for sulfonic acid functionalization by two methodologies including one-pot organosilylation (CFA_CSPTMS) and two-step benzyl alcohol condensation followed by sulfonation (CFA_BnSO3H). The as-prepared organosulfonic CFAs were characterized by solid-state H-1, C-13 and Si-29 NMR spectroscopy, XPS, S content was quantified by elemental analysis and the intrinsic acidity was determined by potentiometric titration; the highest -SO3H content was obtained for CFA13_BnSO3H. All the functionalized CFAs were tested for the first time as acid solid catalysts in the esterification of levulinic acid (LA) a biomass platform molecule, in the presence of n-butanol. n-Butyl levulinate was the only product with conversions of 100% after 40 min. reaction and using the CFA13_BnSO3H as catalyst. This catalyst also exhibited the highest TOFs (447 h(-1)) and showed to be the most stable and reusable for 5 consecutive catalytic cycles.