The invention discloses a preparation method of zinc oxide@zinc micro-spheres. The micro-spheres are prepared by the aid of a laser ablation technique. The preparation method includes the steps: 1) starting a laser, adjusting the position of a lens and focusing laser beams on the surfaces of zinc target materials; 2) dripping solution on substrates until the substrates are completely laid; 3) adjusting output power of the laser to reach 150-300mW, and ablating the zinc target materials for 2-10min in normal-temperature air; 4) drying the substrates at the temperature of 60 DEG C under vacuum to obtain the zinc oxide@zinc micro-spheres on the substrates. The method is simple and easy to operate, the requirement of laser ablation in the air for experimental conditions are reduced, the zinc oxide@zinc micro-spheres with core-shell structures can be prepared in indoor-temperature air environments, and the prepared zinc oxide@zinc micro-spheres have micro-scale diameters, spherical shapes with smooth surfaces and obvious laser characteristics.