A mild, rapid, and efficient method for the solvolysis of sterically hindered esters under high pressure is described. Transesterification is carried out in the presence of DBU at room temperature and at a pressure of 10kbar to give quantitative conversions within short reaction times. The substrates examined included aromatic and aliphatic esters of sterically hindered alcohols and phenols. An optically pure benzyl ester of phenylalanine was chosen to study racemization of the amino acid esters under high-pressure reaction conditions.