A QSPR study was realized in order to predict the Retention Times (RT) determined from interaction between two types of solutes (alcohols and esters) and six Stationary Phases (SPs), five of them specials (1a–e) and a classical one (OV-25), by correlating the adjusted RTs, determined for each SPs at temperature between 70 and 140 °C with the values of molecular descriptors implemented in CODESSA program. New topological indices RAF (for alcohols) and ΔA (for esters) derived from local invariants of chemical graphs of alcohols and esters determine an increase in predictive power of models where these descriptors have been used.