Quantum chemistry parameters of 20 substituted phenols were computed at the 631G* level using DFT method. Based on theoretical linear solvation energy theory, the correlation equation that can predict the retention index (RI) was developed using structural parameters of 15 substituted phenols with experimental data as theoretical descriptors, and the conventional correlation coefficient (R2) is 0.9885. The correlation degree of each independent variable in the model was validated by variance inflation factors (VIF) and t-test. Cross-validation indicates that the model possesses high predicting ability. The correlation and predicting ability of the RI equation are both more advantageous than those based on orientating group index, connectivity index, and topological index method. In addition, RI values of 5 compounds without experimental data were predicted with the model.