The electronic properties of InSe/M (MPd, Au) interfaces have been studied by X-ray photoemission measurements. For the InSe/Pd interface, it has been found that Pd atoms diffuse into the InSe lattice at early stages of Pd coverage, acting as acceptor centers. As the Pd coverage increases, a Pd–InSe reaction determines the electronic behaviour of the interface. However, for Pd coverages higher than 1ML, the barrier formation tends to be controlled by an emerging bulklike Pd overlayer. Despite the atomic structure of this system is far from that expected for an ideal Schottky one, the final electronic barrier value is close to that expected for an abrupt InSe/Pd Schottky interface. On the contrary, the InSe/Au system appeared to behave as a quasi-ideal abrupt Schottky interface. Annealing processes performed at temperatures higher than 600K alter this scheme, as revealed by X-ray absorption spectroscopy measurements, enhancing diffusion of Au atoms into InSe. In any case, the electronic barrier results to be determined by the Au overlayer formed.