Composite ceramic materials based on B4C with the addition of TiB2 in amounts of 0, 10, 20, 25 and 30 mol. % have been studied. Titanium diboride was synthesized from TiO2 powder and nanofibrous carbon using the boron carbide method in an induction furnace at 1650 °C in an argon atmosphere. The samples were produced by hot pressing at 2100 °C and 25 MPa in an argon environment. The phase composition was determined, and the apparent density and open porosity of the experimental materials were measured. The microstructure was assessed using optical and scanning electron microscopy. The investigations revealed that an increase in the TiB2 content reduces the open porosity while concurrently enhancing the relative density of the boron carbide ceramics. For a sample containing 30 mol. % TiB2 , the open porosity and relative theoretical density were 1.6 and 99 %, respectively. Using XRD and XRS analyses established that the synthesized materials are comprised of two phases: B4C and TiB2 . The average grain size of TiB2 was 0.85 ± 0.02 µm for the sample with 10 mol. % TiB2 and 8.90 ± 0.25 µm for the material with 30 mol. % TiB2 . It was found that at higher TiB2 concentrations, large clusters of grains are formed. The destruction pattern of B4C grains is intragranular, while TiB2 grains are characterized by intergranular destruction. For a sample containing 30 mol. % TiB2 , the fracture toughness was 4.97 ± 0.23 MPa∙m0.5, and the hardness was 3320 ± 120 HV0.5 . Therefore, the addition of TiB2 at these specified concentrations facilitated a 30 % enhancement in fracture toughness relative to single-phase B4C while preserving a high level of hardness.