X-ray diffraction analysis of the Fe-35%FKh800-(0.38-2.2%)TiB2 system samples showed that a multiphase composition of materials is formed during the sintering process. The basis of the sintered composite is the ferrite α-Fe phase, which is a metallic ironchromium matrix, with γ-Fe, complex iron-chromium carbide (Fe,Cr)7C3, and carboboride phases in small amounts: borocementite – Fe3(B0.7,C0.3) with a rhombohedral lattice and carboboride Fe23(C,B)6 with a cubic lattice and a number of carbides (Cr7C3, Cr3C2). The research established the non-monotonic nature of the effect of the TiB2 additive content on the lattice parameters of the ferrite α-Fe and austenitic γ-Fe phases, as well as on the change in the intensity of the 111 line of the austenitic phase. According to the phase composition data and studies of the fine structure (substructure) of the sintered samples of the Fe-FKh800-TiB2 system materials, it can be noted that the components of the TiB2 alloying additive take an active part in the formation of the phase composition, as well as in the process of alloying the matrix phase, which is reflected in the numerical values of the substructure parameters.