We have investigated xNi–yCu–ZrO2 catalysts for the selective synthesis of γ-valerolactone from levulinic acid (LA). A series of xNi–yCu–ZrO2 catalysts with a consistent metal loading of 50% but varying Ni and Cu composition were prepared by an oxalate gel precipitation method and tested for LA hydrogenation. Ni-rich catalysts showed higher catalytic activity compared with Cu-rich formulations with a 45Ni–5Cu–ZrO2 composition yielding 76% γ-valerolactone after a reaction time of 30 min at 200 °C. Characterisation of the materials by XRD, surface area measurements and TPR allow us to attribute the differences in performance seen for different compositions to particle size and nanoparticle dispersion effects. DFT calculations also showed that a shift of d-band centre to higher energies with the mole fraction of Ni in Cu–Ni alloys would be expected to lead to improved hydrogen dissociation in Ni-rich catalysts and so aid hydrogenation activity.