The ZrW2O8 ceramic was successfully synthesized by laser sintering for the first time in this work. The microstructure observation by a scanning electron microscope shows that crystalline grains of the ZrW2O8 ceramic samples are fine and homogenous and that their size is about 10 nm. The analyses by an X-ray diffractometer and Raman spectrometer exhibit that only α-ZrW2O8 exists on the outside but both α-ZrW2O8 and γ-ZrW2O8 exist in the bulk of the sample. It is also confident of that ZrW2O8 ceramics can be effectively synthesize by laser sintering. The existence of γ-ZrW2O8 in the bulk may be due to the huge stress generated in the laser sintering processing. Moreover, the effect of laser scanning velocity on the properties of ZrW2O8 ceramic was analyzed. It is indicated that the amount of γ-ZrW2O8 in the bulk could be effectively cut down by means of appropriately reducing scanning velocity and optimum laser power density.