The semi-empirical electrotopological index, I(SET,) used for QSRR models, was developed and optimized to describe the chromatographic retention of saturated esters on the five different stationary phases (SE-30, OV-7, DC-710, OV-225 and XE-60). The simple linear regressions between the retention indices and the proposed index were of good statistical quality, high internal stability and good predictive ability for external groups, especially for the stationary phase with low polarity, showing that the specific molecular interactions occur on highly polar phases. For the esters, the interactions between the molecules and the stationary phase are slowly increased relative to hydrocarbons due to the charge redistribution that occurs in the presence of the heteroatom. These facts were included in the calculation of I(SET) through a small increase in the SET(i) values for heteroatoms and the carbon atoms attached to them. The increase in the SET(i) values originates from the dipole moment of the whole molecule and an equivalent local dipole moment related to the net charges of the atoms belonging to the functional group and the carbon atoms attached to them. The polarity of the stationary phases, indicated by the retention polarity (P(R)) given by Tarján, is reflected in the intercept of the equations obtained for each stationary phase. Thus, a single combined QSRR model was generated with a satisfactory predictive quality, including a parameter that represents the polarity retention of all stationary phases studied.