The synthesis of undecylenic acid partial esters can be performed at mild temperature with a classical esterification reaction catalyzed by dodecylbenzene sulfonic acid (DBSA). A semi‐empirical molecular modeling on the different reaction intermediates indicates that DBSA can strongly decrease their heats of formation through hydrogen bonding. Diester formation seems to be thermodynamically favored with a selectivity for alpha, alpha, or alpha, beta forms that depend on the geometry of the catalyst‐intermediate configuration. Triesters are not favored but a high selectivity for monoesters requires a kinetic control. Experimental approach, considering different DBSA concentrations and temperature partially confirms the theoretical predictions but surfactant properties of DBSA and monoesters may induce nonpredicted geometries. Global apparent activation energies are calculated, corresponding to the formation and hydrolysis of mono and diesters. If water trapping allows the decrease of hydrolysis reaction constants, the presence of water and subsequent phase separation may explain differences between theoretical and experimental results and could help increasing monoester selectivity.