Phenolic esters are considered as promising functional food ingredients. However, their digestion, absorption and metabolism are still unclear. Tyrosol acyl esters (TYr-Es), hydroxytyrosol acyl esters (HTy-Es) and alkyl gallates (A-GAs) were hydrolyzed by carboxylesterase in plasma and exhibited slow release of polyphenols (phenolic acids). In vitro hydrolysis degrees initially increased and then decreased with the increasing carbon chain length (C2-C16). TYr-Es exhibited higher hydrolysis degrees compared to HTy-Es, and hydrolysis degrees of TYr-Es and HTy-Es were markedly higher than those of A-GAs. Due to the fast hydrolysis rates of TYr-Es and HTy-Es, they were undetectable in all rat plasma samples collected at several times within 24 h after administration. Whereas, A-GAs could be detected in rat plasmas and three absorption peaks were found in the pharmacokinetic profiles. Importantly, the T1/2, MRT, AUC0-∞, AUC0-t in octyl gallate group were longer (or stronger) than those in propyl gallate and dodecyl gallate groups.