The method of laser treating Ti-6Al-4V to form surface compounds is a method of forming barrier layers on surfaces of Ti-6Al-4V workpieces. The Ti-6Al-4V workpiece is first cleaned and then a water-soluble phenolic resin is applied to at least one surface of the Ti-6Al-4V workpiece. The Ti-6Al-4V workpiece and the layer(s) of water soluble phenolic resin are then heated to carbonize the phenolic resin, thus forming a carbon film on the at least one surface. TiC particles are then inserted into the carbon film. Following the insertion of the TiC particles, a laser beam is scanned over the at least one surface of the Ti-6Al-4V workpiece. A stream of nitrogen gas is sprayed on the surface of the Ti-6Al-4V workpiece coaxially and simultaneously with the laser beam at a relatively high pressure, thus forming a barrier layer of TiCxN1-x, TiNx, Ti—C, and Ti2N compounds in the surface region.