The differential thermal analysis and X-ray diffraction measurements show that on cooling Li2B4O7 melt generally undergoes transition to glassy state. It is also found that the material can be transformed into single crystal form by applying suitable growth rates. An analysis of these results shows that the microstructure of the molten state is an important factor governing the transition to the two forms on solidification. (C) 2004 Elsevier B.V. All rights reserved.