The improvement of the combustion process in gasoline spark engines has been a painstaking task focused on developing chemical compounds. These ones have to be capable of bettering the engine performance and meeting standards set by environmental and health regulations aimed at reducing the emission of hazardous pollutants. Among the molecules synthesized for reaching these goals, oxygenating agents have been used to increase the octane number and make more efficient the combustion reaction by reducing the emissions of CO, polyaromatic hydrocarbons (PAHs), and particulate matter. As a result of this quest, MTBE has been used as a solution, but in recent years, negative effects of its use polluting water bodies and, as a consequence, the human health, have proven the opposite. For this reason, alternative oxygenating compounds to MTBE such as alcohols, ethers, and esters are being studied. According to the aforementioned, in the present paper, alternative oxygenating agents belonging to glycerol acetates (GAs) were synthesized from crude glycerol (CG) obtained as a biodiesel by-product and conditioned as starting material to perform esterification reactions with acetic acid or acetic anhydride. In order to assess the performance of these compounds as octane index enhancers, measurements using the same composition of ethanol, MTBE and the as-obtained GAs, in reference gasoline, were made, yielding comparable results that encourage the potential use of acetins as a replacement of MTBE.