Copyright © 2018 American Chemical Society. Herein we demonstrate that the photolabile protecting group (PPG), the 1-[3-(diethylamino)-phenyl]ethyl (DEAPE) group, has dramatically different photochemical properties from the parent 3-(diethylamino)benzyl (DEABn) PPG. The new PPG, derived from DEABn by adding a methyl group to the benzylic carbon, has similar reactivity as DEABn in releasing alcohol in MeCN/water; however, it is more efficient than DEABn in releasing carboxylic acid. In particular, it can release carboxylic acid efficiently in aprotic solvents and the PPG itself converts to 3-diethylaminostyrene. Photochemical removal of DEAPE can also be conveniently carried out with sunlight. The results in this work suggest that there probably exist multiple reaction pathways in cleaving the benzylic C-O bond and they can be affected by the benzylic substitution and the reaction conditions.