TiB2/BN multilayers with the modulation ratios (t(TiB2):t(BN)) ranging from 1:1 to 16:1 and a constant modulation period of 24 nm were prepared by magnetron sputtering. The TiB2/BN multilayers were subsequently annealed in a vacuum environment at temperatures of 500-700 degrees C for 30 min, then characterized by extensive measurements. All multilayers exhibited small grain sizes and stable layer structures with polycrystalline with TiB2(001), TiB2(101), TiB2(002) textures or amorphous BN, resulting in higher hardness and elastic modulus than that of individual monolithic TiB2 or BN coatings. The hardness of as-deposited multilayer can reach as high as 39.34 GPa at t(TiB2):t(BN) = 13:1, meanwhile the friction coefficient got to 0.028, which was also the lowest. The hardness and friction were almost unchanged after annealing at 500-700 degrees C, which was attributed to good thermal stability in the layer structure and the existence of stable TiBxNy phases. (C) 2012 Elsevier B.V. All rights reserved.