The thermochemical treatment applied to improve the surface properties of AZ91 consisted in heating the material in contact with AlSi10Mg powder at 445 oC for 30 min. During heat treatment process the powder was held under pressure to facilitate the diffusion of the alloying elements to the substrate and, accordingly, the formation of a modified layer. Two pressures, 1 MPa and 5 MPa, were tested. The resultant layers, containing hard Mg2Si and Mg17Al12 phases, were examined using an optical microscope and a scanning electron microscope equipped with an energy-dispersive X-ray spectrometer (EDS). The experimental data show that the layer microstructure was dependent on the pressure applied. A thicker, three-zone layer (about 200 μm) was obtained at 1 MPa. At the top, there were Mg2Si phase particles distributed over the Mg17Al12 intermetallic phase matrix. The next zone was a eutectic (Mg17Al12 and a solid solution of Al in Mg) with Mg2Si phase particles embedded in it. Finally, the area closest to the AZ91 substrate was a eutectic not including the Mg2Si phase particles. By contrast, the layer produced at a pressure of 5 MPa had lower thickness of approx. 150 μm and a two-zone structure. Mg2Si phase particles were present in both zones. In the upper zone, Mg2Si phase particles were regularly distributed over the Mg17Al12 intermetallic phase matrix. The lower zone, adjacent to the AZ91, was characterized by a higher volume fraction of Mg2Si phase particles distributed over the matrix composed mainly of Mg17Al12. The alloyed layers enriched with Al and Si had much higher hardness than the AZ91 substrate.