The retention factor (k) and retention index (I) of homologous series compounds such as alkylbenzenes (BZ), alkylaryl ketones, alkylbenzoates, and alkylparabens in microemulsion electrokinetic chromatography (MEEKC) with suppressed electroosmosis were investigated in a wide range of SDS concentrations ([SDS]), temperatures, and concentrations of organic cosolvents (phi). Using BZ as standards, the retention indices of other homologous series compounds were determined and they were found to be independent of [SDS] and temperature, while are dependent on the types and concentrations of organic cosolvents. The retention factor linearly increases with increasing [SDS], while linearly decreases with increasing temperature. The value of log k linearly decreases with increasing phi for methanol, ethanol, or ACN, while decreases by a second-degree polynomial with increasing phi for 2-propanol. Excellent agreement was found between the observed and predicted values of log k of analytes in MEEKC at given [SDS] and phi, where the predicted values were obtained from modified equations of the linear relationship of log k as functions of [SDS], the number of carbons, and phi. Therefore, both k and I can be used for peak identification of homologous series compounds.