The process of sucrose esterification in the presence of a homogeneous catalyst was developed directing the reaction to the production of weakly substituted esters. Esterification of sucrose was processed with octanoyl chloride in a discontinuous reactor, in presence of 4-dimethylaminopyridine as catalyst. The process was operated in a time interval ranging from 0 to 80 min, at temperatures from 288 to 303 K, pH=10 and at atmospheric pressure. The following conversion levels were obtained: octanoyl chloride 11-84%, primary monoester production of 9-67%, secondary monoesters of 1.3-17%. Activation energies ranging from 158 to 300 kJ/mol characterized the stages of the process, among them the stage of formation of the DMAP/RCOC1 complex (162.43 kJ/mol). The increase in primary monoesters yield due to the temperature rise, leads to an increase in the rate of the direct reaction as well as in the speed of secondary monoester conversion to primary monoesters, quantifying a selectivity in primary isomers in the following positions sequence: 6> 1' > 6'.