The structurization of Fe–Mo alloys at 5–30 wt.% Mo is studied and contact interaction of these alloys with titanium diboride is examined. The Fe–5 wt.% Mo and Fe–9 wt.% Mo alloys consist of an α-Fe metallic structure with inclusions of Fe2Mo intermetallics. The Fe–13% Mo alloy based on the α-Fe solid solution contains individual inclusions of Fe3Mo2 intermetallics. When Mo content of the alloys increases to 17–30 wt.%, Fe2Mo and Fe3Mo2 intermetallics form intensively and make the alloy brittle. Zero contact angles are observed for the (Fe–13 wt.% Mo) and (Fe–17 wt.% Mo) alloys. The TiB2–(Fe–13 wt.% Mo) system is characterized by chemical interaction leading to additional molybdenum, iron, and titanium boride phases. The TiB2–(Fe–13 wt.% Mo) system shows no brittle intermetallic phases. The contact interaction in the TiB2–(Fe–17 wt.% Mo) system leads to the intensive formation of complex molybdenum–iron–titanium borides; there is also a great number of Fe3Mo2 intermetallics. The TiB2–(Fe–13 wt.% Mo) system is promising for the development of new composite materials and coatings with high wear resistance.