Three kinds of laser boronizing composite coatings were in situ synthesized on Ti substrate by using powders of B, BN and B4C as starting materials. Microstructures of the laser boronizing composite coatings were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM); and their worn surface morphologies were also observed by using SEM. Moreover, the friction and wear behavior of the boronizing composite coatings under dry sliding condition were evaluated using a UMT-2MT friction and wear tester. It was found that all the three types of laser boronizing composite coatings had higher microhardness and better wear resistance than pure Ti substrate; and their microstructure and wear resistance varied with varying pre-placed powders of B, BN, and B4C. Under the same dry sliding test conditions, the wear resistance of the three kinds of laser boronizing composite coatings, i.e., sample 1 prepared from pre-placed B, sample 2 obtained from pre-placed BN, and sample 3 fabricated from pre-placed B4C, is ranked in an order of sample 1 > sample 2 > sample 3, which, surprisingly, well conforms to their order of hardness and friction coefficients. (c) 2010 Elsevier B. V. All rights reserved.