Nanometer scale TiN/TiB 2 multilayer coatings with a thickness of approximately 2 μm could be deposited on steel substrates using PECVD. The coatings were prepared by alternate depositions of TiN and TiB 2 using a gas mixture of TiCl 4 , H 2 , Ar, N 2 and BCl 3 . The TiN grain size increased with increasing TiN layer thickness, while changes in the TiB 2 layer thickness had no significant influence on the microstructure of the TiB 2 layers. The plastic hardness of the coatings increased steadily with decreasing TiN layer thickness and with increasing TiB 2 layer thickness. No significant change in hardness was observed with changes in the layer period. The hardness values of the multilayer coatings had a linear relationship with the TiB 2 volume fraction. Therefore, the maximum hardness value of the multilayer coatings did not exceed that of the monolayer TiB 2 coating. The wear resistance, however, increased by incorporating TiN layers. It was found that multilayer coatings with periods <24 nm showed better wear resistance than the monolayer coatings. It is believed that the wear resistance of the multilayer coatings was improved as crack propagation could be interrupted at the layer interface and the size of the debris detached from the coating could be reduced.