In order to endow Poly-ether-ether-ketone (PEEK) with good surface conductivity and realize its application in radar antenna and other aerospace fields. PEEK with high chemical inert was modified by 1064nm-wavelength infrared pulse fiber laser, then deposited with Ni-P alloys by means of electroless plating technology. The properties of surface metal layers on PEEK were characterized by SEM, resistance tester and metallographic microscope, respectively. When the laser energy density was relatively low (Q<60 J/cm2), there was mainly photothermal effect on the surface of PEEK by pulsed laser, and the surface of the substrate presented periodic undulating groove structure with a small number of holes. When the laser energy density was rather higher (Q≥60 J/cm2), there were simultaneously enhanced photothermal effect and partial photochemical effect. As a result, the surface of PEEK was 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>10 J/cm2), of which the surface resistance of the coating was less than 20 mΩ. In this paper, the interaction mechanism of the pulse laser on PEEK surface is studied and the metals on the PEEK have been prepared under the laser-induced effect.