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A two-step process was developed for the preparation of triacetylglycerol (TAG), a biofuel additive employing a solid acid catalyst derived from glycerol. The first step involves esterification of glycerol with acetic acid (1:4 mol) at 115 °C for 1 h in the presence of catalyst (5 wt %) to obtain 100% conversion of glycerol with 22, 67, and 11% MAG, DAG, and TAG, respectively. In the second step, the esterified product mixture after removal of excess acetic acid and moisture was acetylated with acetic anhydride (1 mol with respect to glycerol) at 115 °C for 30 min to obtain 100% TAG. The recovered catalyst was reused for five cycles without any significant loss of its initial activity. The protocol is cost-effective due to the use of highly stable and recyclable SO3H-carbon catalyst for the production of TAG with minimum moles of acetic acid and acetic anhydride in shorter reaction time.