In this paper we report the preparation of double carbide (Ti,Cr)C with a chromium content of 10 ÷ 30 at% by electrothermal explosive synthesis (ETE). This method allows synthesis to be carried out at high temperature with minimal holding time. The ETE method is favourable for the formation of dense carbide ceramics. The synthesized samples were characterized by X-ray diffraction and scanning electron microscopy. It was found experimentally that the unit cell parameter of the double carbide decreases linearly with increasing chromium content. The DFT calculations also confirmed the dependence of the unit cell parameter (Ti,Cr)C on the chromium content according to Vegard's law and show changes in the cell shape and distance between Cr–Cr layers with increasing chromium content. The pDOS diagram shows that an increase in chromium content leads to an excess of d∗ electrons on the π∗ orbitals, which has a destabilizing effect on the double carbide structure.Crystal Orbital Hamiltonian (COHP) analysis of the electronic structure of the double carbide, partitioning the energy of the band structure into bonding, non-bonding and anti-bonding energy regions, showed the influence of chromium content on its stability.