An alternative nickel-based catalyst for the aerobic debenzylation of benzyl ethers has been devised in order to provide a complement to the well-known hydrogenolysis strategy as well as to other reductive or oxidative procedures, including vanadium-catalyzed cleavage under molecular oxygen. A systematic study of reaction conditions has led to an optimized procedure from (pentyloxy)methyl)benzene (POMB) that provides selectively target 1-pentyl alcohol (PA), releasing the benzyl group as benzoic acid (BA). The participation of homogeneous species is supported by several experiments, which also reveal the intermediacy of pentyl benzoate.