The matching property of polycrystalline wafers phosphorus diffusion and laser doping process was studied. Nanosecond pulsed laser with a wavelength of 532 nm was used to conduct laser scanning doping on polycrystalline wafers which remains phosphorosilicate glass after diffusion. The sheet resistance decreases about 50%, and with the increasing of laser power, more phosphorus atoms diffuse to polycrystalline silicon, and the sheet resistance decreases more significantly. The external quantum efficiency of the conventional solar cells and laserdoped solar cells was tested, and for the band of 340~480 nm, the EQE of laserdoped cells increased by 18% to 5% compared to the conventional solar cells. The photoelectric conversion characteristics of laserdoped polycrystalline silicon cells were studied, and the failure characteristics under high laser power were analyzed. With the using of optimization of laser doping polycrystalline silicon solar cell process technology, the average photoelectric conversion efficiency of solar cells achieves 17.11%, which is 0.34% higher than that of the conventional cells. The highest efficiency achieves 17.47%. Laser doping process is simple, and conversion efficiency increases significantly, so this process makes it easy to realize industrialization.