The crystallization behavior of LiB3O5 (LBO) has been investigated by performing differential thermal analysis (DTA). When the measurements are carried out with the highest temperature limited to a few degrees above the melting point, a clear indication of the crystallization is revealed by the presence of exotherms at 787 °C and 772 °C in the DTA plot. On the other hand, the crystallization of LBO phase gets inhibited if the melt is subjected to a much higher temperature, prior to cooling. Powder X-ray diffraction patterns recorded in the two cases are also in agreement with these observations. The results obtained have been explained in terms of the microstructure of the melt, which besides other factors, is shown to be dependent upon the highest temperature to which the melt is raised prior to crystallization. The inference drawn has been vetted by growing LBO single crystals by to pseeded solution growth technique. The results obtained also hel pto understand the difficulties encountered in nucleating LBO from a boron-rich solution with a Pt wire, as reported in literature [1].