High-temperature X-Ray diffractometric (HTXRD) and dilatometric studies of lithium berates, namely Li3BO3, alpha-Li4B2O5, beta-Li4B2O5, Li6B4O9, alpha-LiBO2, Li2B4O7, Li3B7O12 LiB3O5, and Li2B8O13 have been carried out, which revealed that Li2B8O13 underwent a solid-phase transition from triclinic to monoclinic at temperatures >543 K in air. The variation in lattice parameters with temperature, unit-cell volume as well as Linear coefficient of thermal expansion (alpha(a), alpha(b) and alpha(c)), volume expansion of the unit cell (alpha(v)) of the compounds as well as bulk thermal expansion coefficients have been determined by HTXRD and dilatometry respectively.