A new series of esters was prepared by esterification of 1, 4:3, 6-dianhydro-D-glucitol with long chain fatty acid chlorides. The experimental conditions prevented thermal degradation of the sugar and led to diesters with a high degree of purity. The final products were readily isolated and characterized by IR and NMR. Molecular modelling confirmed that the exo and endo configurations of the o-alkyl groups of the diesters of isosorbide were retained. This work reports a novel synthesis of diesters of natural origin which shows promise in environmentally sensitive applications, such as phytosanitory adjuvants, requiring biodegradable materials as replacements for fossil-derived products.