Ongoing active development of modern radio frequency electronic devices operating in the millimeter (V) band, such as fifth-generation wireless communications, demands new materials to control electromagnetic interference, compatibility, and reliability of such systems. This work investigates feasibility absorptive non-reflective thin coatings deposition on dielectric substrates using simultaneous magnetron co-deposition. For this, electromagnetic waves propagation in the millimeter band through in micrometer-thick Al–Si films of varied composition was studied. The co-deposition process was controlled by the ratio of sputtered atoms fluxes. Graded segregation was observed under certain parameters of the co-deposition process, resulting in a depth gradient of an aluminum content, as confirmed by the secondary ion mass spectrometry study. A qualitative model was proposed involving aluminum-induced silicon recrystallization happening in the course of a known aluminum interlayer exchange process. The observed Al–Si segregation effect in micrometer-thick films allows for preparation of the non-reflective and absorptive material for operation in the V-band with reflection losses more than 10 dB and transmission losses around 5 dB in the bandwidth of up to 20 GHz.