Methods of spontaneous crystallization on a platinum loop, modified VPA method, solid phase synthesis. X-ray powder diffraction analysis and chemical analyses were used to study phase formation in the Li, Ba//BO2, F ternary reciprocal system and the base of the BaO-B2O3-Li2O prism of quaternary reciprocal system Ba, B, Li//O, F. In these systems the fields of primary crystallization of beta-BaB2O4 were determined and a promising solvent for crystal growth was found. A series of experiments were carried out on the growth of bulk barium borate crystals in the system BaB2O4-LiF. (C) 2014 Published by Elsevier B.V.