The esterification process of ethenyl benzene and its derivative compounds (p-methyl, p-methoxy, p-chloro, m-methyl, m-nitro and m-chloro, respectively) was carried out with acetic acid and using perchloric acid as a catalyst. From the effects of the variables studied it could be concluded that: the temperature and the catalyst concentration influence positively over the olefin conversion, whereas the initial olefin concentration exert no effect over the same; and that the presence of perchloric salts exerts a different influence, depending on the temperature and on the catalyst concentration. It has been proven that the substituted radicals in the m- or p-positions exert an important influence over the conversion of the studied olefins, presenting growing reactivity in the following order: m-nitro ethenyl benzene, m-chloro ethenyl benzene, p-chloro ethenyl benzene, m-methyl ethenyl benzene, ethenyl benzene, p-methyl ethenyl benzene and p-methoxy ethenyl benzene. Finally, a kinetic and thermodynamic study has been done and the corresponding parameters have been calculated, with an adequate fitting.