Recent studies have shown that the electromagnetic shower induced by a high-energy electron, positron or photon incident along the axis of an oriented crystal develops in a space more compact than the ordinary. On the other hand, the properties of the hadronic interactions are not affected by the lattice structure. This means that, inside an oriented crystal, the natural difference between the hadronic and the electromagnetic shower profile is strongly accentuated. Thus, a calorimeter composed of oriented crystals could be intrinsically capable of identifying more accurately the nature of the incident particles, with respect to a detector composed only of non-aligned crystals. Since no oriented calorimeter has ever been developed, this possibility remains largely unexplored and can be investigated only by means of numerical simulations. In this work, we report the first quantitative evaluation of the particle identification capability of such a calorimeter, focusing on the case of neutron-gamma discrimination. We demonstrate through Geant4 simulations that the use of oriented crystals significantly improves the performance of a Random Forest classifier trained on the detector data. This work is a proof that oriented calorimeters could be a viable option for all the environments where particle identification must be performed with a very high accuracy, such as future high-intensity particle physics experiments and satellite-based γ-ray telescopes.