Si3N4–Ni60 is firstly used to improve the wear resistance of a TA7 (Ti–5Al–2.5Sn) titanium alloy surface by mean of a laser alloying (LA) technique. The synthesis of the hard composite coating on a TA7 titanium alloy by LA of Ni60–Si3N4 pre-placed powders was investigated by means of scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and high resolution transmission electron microscope (HRTEM). Experimental results indicated that a number of the interdendritic lamellar eutectics, nanoscale ceramics (NC) and the amorphous phases were produced in such LA coating. The production of NC led the free energy to enhance, which increased the density of point defect, leading to the formation of hypersaturated state of point defect, causing lattice distortions. Compared with a TA7 alloy substrate, an improvement of the wear resistance was obtained for such LA composite coating.