Ethylene was thermocatalytically transformed into carbon products via a CCVD process. The filamentous carbon obtained was further modified with concentrated sulfuric acid or 4-benzenediazonium sulfonate (BDS) to produce acid-type catalysts. The as-prepared samples were characterized by SEM and TEM techniques to confirm their morphological features. TG, XRD, elemental, and porosity analyses were also performed to assess the quality of these materials. The fabricated carbons were tested in eco-friendly green synthesis of value-added fuel bio-additives, namely in glycerol esterification. The reaction of glycerol transformation was performed with acetic acid at 80 °C using different glycerol to acetic acid (Gly/AA) molar ratios. The samples functionalized with diazonium salt showed better performance in the above process than those modified with H2SO4, and this was found to be directly related to the degree of surface functionalization with acidic sites. BDS-modified carbon fibers allowed obtaining acceptable results within 6 h when the reaction was performed with a Gly/AA molar ratio of 1:6, however, the dominant products in this case were mono- and diacetins. Extended reaction time altered the distribution of products. Finally, the combined selectivity to the targeted acetins (i.e., DA and TA) was about 75.5%. A direct correlation between the content of -SO3H groups of CNFs and the yield of higher acetins was found.