The role of structural relationships between metal-solvent and nearest intermetallic compound on the formation of extended solid solutions obtained by mechanical alloying was investigated. The systems Ni-Ga, Ni-Ge, Ni-In and Ni-Sn were studied. It was found, that if the host metal and the intermetallic compound adjacent to the solid solution have structural relationship, mechanical alloying allows one to extend the range of the nickel-based solid solutions. It was shown that supersaturated solid solutions extend to the two-phase regions and the region of the intermetallic compound at a favorable size factor.