The phase diagram of a four-component reciprocal system Na, K‖Cl, BO2, CO3 into simplexes was triangulated, the main dominant chemical exchange reactions were revealed. It is shown that in a four-component reciprocal system, Na, K ‖ Cl, BO2, CO3, continuous rows of solid solutions based on sodium and potassium metaborates NaхК1-хBO2, sodium and potassium carbonates NaхК1-хСO3 are stable and do not disintegrate with the formation of eutectic. The phase diagram of the stable NaBO2-Na2СO3-КBO2-К2СO3-КCl pentatope of a four-component reciprocal system Na, К‖Cl, BO2, and CO3 was studied for the first time using the method of differential thermal analysis. It is shown that melts of a four-component reciprocal system Na, K ‖ Cl, BO2, CO3 can be used as media for the synthesis of oxide tungsten bronzes.