The structure and dynamics of alkan-1-ol/alkylbenzoate binary mixtures have been studied by microwave dielectric relaxation spectroscopy in the 200 MHz to 20 GHz frequency range. The binary mixtures of methanol, ethanol, propan-1-ol, butan-1-ol, and pentan-1-ol with methyl, ethyl, propyl, and butyl benzoates were studied at 298.15 K The relaxational response of the pure alcohols, pure esters, and their binary mixtures over the full composition range is properly described by the Havriliak-Negami model. The alcohol content, alcohol length, and alkyl side-chain effects on the relaxational properties have been studied for these mixtures over the whole composition range. From the experimental readings, the effective and the corrective Kirkwood and Bruggeman correlation factors have been calculated. The data gathered have been interpreted in terms of the alkyl side-chain effect and their reliance on the mixture composition.