The solid-phase mechanical synthesis of high-nitrogen ferritic and austenitic steel composites in the course of mechanical activation in a ball mill is studied by the method of Mössbauer spectroscopy and electron microscopy. For mechanical alloying, mixtures of iron alloys doped with transition metals (Ni, Cr, Mn, and Ti) and nitrides with low stability to deformation (CrN and Mn2N) were used. The correlation between the phase–concentration composition of the mechanically synthesized samples and the heat of formation of transition metal nitrides, which are part of the initial metal mixtures, is investigated. It is established that the use of titanium as an alloying additive of the Fe component of the mixture accelerates the processes of dissolution of primary nitrides and allows the transference of chromium and manganese to the position of substitution in the metallic solid solution. In addition, the titanium additive entails the formation of secondary nitrides with stabilizing the nanostructure of the mechanically synthesized samples.