Boron carbide-based materials B4C-MexBy were densified by pressureless sintering in a vacuum furnace. Some transition metal carbides (TiC, ZrC, HfC, Cr3C2 and WC) from groups IV-VI were used as sintering aids. The optimal sintering temperature in the range 2220-2250oC was used for any composition. Here we show the possibilities to activate the mass transport of the B4C by the mechanism of liquid phase sintering. The method of reactive sintering of B4C in the presence of additives of some transition metal carbides allows in situ synthesis of dense B4C-MexBy materials. Structural properties and fracture toughness of the B4C-based composite materials were discussed. The properties of some of these materials and the possibilities for their application are also discussed.