Uniform orthorhombic Li3B5O8(OH)(2) micro-rods were hydrothermally synthesized at 150-210 degrees C for 6.0-24.0 h, using LiOH center dot H2O and H3BO3 as the reactants. The resulting Li3B5O8(OH)(2) micro-rods had a length of 20-60 mu m, an aspect ratio of 6-14, and a high crystallinity. The presence of hexadecyl trimethyl ammonium bromide was favorable for the oriented growth of the Li3B5O8(OH)(2) micro-rods. The orthorhombic Li3B5O8(OH)(2) was decomposed into Li2B4O7 and alpha-LiBO2. Pore-free high crystallinity Li2B4O7 with quasi polyhedron morphology can be obtained by NaCl assisted calcination. This enlarged the controllable synthesis of the alkali borates, especially enriched the study on the lithium borates which can be potentially used as a perspective superionic conductor and electrode of lithium ion batteries. (C) 2011 Elsevier B.V. All rights reserved.