A process is described for preparing esters of an acid component selected from among polybasic C.sub.4-C.sub.10 carboxylic acids and an alcohol component selected from among C.sub.3-C.sub.12 alkanols or from among C.sub.3-C.sub.12 alkanediols, the alkyl chain of which may have interruption by from 1 to 3 oxygen atoms, by a) heating at boiling point, in a reaction zone and in the presence of an esterification catalyst, a mixture essentially consisting of the acid component or of an anhydride thereof and of the alcohol component, b) using rectification to separate the vapor comprising alcohol and water into an alcohol-rich fraction and a water-rich fraction, and c) returning the alcohol-rich fraction into the reaction zone and conducting the water-rich fraction out of the process. The process is simple to carry out and permits rapid achievement of essentially quantitative conversion.