Aluminising processes are well-known techniques industrially adopted to enrich of aluminium the surface layers of Ni-based alloys thus improving their resistance to environmental interaction at high-temperature. The results of aluminising processes are typically described in terms of the presence, compositions and thickness of the sequence of layers at the surface of the treated parts. Following this approach, the microstructural features of the diffusion layers obtained under different holding times via vapour-phase type high-temperature low-activity process were experimentally investigated on single crystal CMSX4 alloy. The attention was particularly focused on the effect of the crystallographic orientation of the crystal on the coating features. The evolution of the diffusion layers under different process conditions was then taken into account.