A series of Ni located on hollow spherical ZrO2 catalysts was prepared, and their catalytic performances for octanoic acid deoxygenation were investigated. The ZrO2 hollow spheres saturated by the water phase served as a nanoreactor that captured octanoic acid to react with Ni located inside a hollow spherical ZrO2. The complete conversion of octanoic acid deoxygenation could be achieved by migration of reactants and products in the water-oil biphasic phase. Oxygen vacancies on ZrO2 that resulted from calcination temperature improved the catalytic activity of deoxygenation. Propionic acid was taken as a model compound instead of octanoic acid in view of their same functional group (carboxyl), to study the mechanisms of hydrodeoxygenation, decarbonylation, and decarboxylation through density functional theory of calculations. The main reaction route was decarboxylation which was consistent with the experimental results. (C) 2016 Elsevier B.V. All rights reserved.