We report on an approach for laser surface nitriding of Ti6Al4V alloy coupled with an applied stress field. A surprising finding was that, with increasing the applied stress levels, the decreased residual stress, the nitrogen concentration near the surface, and the surface microhardness of the nitrided layer were associated with the increased friction coefficient. Across the depth of the nitrided layer, the hardness, the elastic modulus, and the wear resistance (H/E) measured by nanoindentation decreased gradually and were ascribed to the gradient of nitrogen concentration in the melt zone.