In order to broaden the application range, PEEK has been modified by 1064nm-wavelength pulse laser, then deposited with Ni-P alloys by electroless plating. The properties of metal layers on PEEK were characterized by SEM, resistance tester and metallographic microscope, respectively. When the laser energy density is relatively low (Q<60J·cm-2), there is mainly photothermal effect on the PEEK with laser, and the surface of the substrate presents periodic undulating groove structure with a small number of holes. When the laser energy density is rather higher (Q≥60J·cm-2), there are simultaneously enhanced photothermal effect and partial photochemical effect. As a result, the surface of PEEK is uniformly covered with melted layer or re-solidified product after melting. Besides, the nickel coatings on the PEEK have been dense, uniform and in good adhesion with the substrate for the sample after laser treatments (Q>10J·cm-2), of which the surface resistance of the coating is less than 20 mΩ. In this paper, the interaction mechanism of the pulse laser on PEEK has been studied and the metals on the PEEK have been prepared under the laser-induced effect, which provides technical support for the future application of PEEK in aviation with aerospace fields, such as, radar and antenna.