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The microstructure of lanthanum hexaboride (LaB6) polycrystalline has been studied by using transmission electron microscopy. This shows that the ideal LaB6 polycrystalline can be obtained by sintering ingots at the temperature of 2273 K for a holding time of 120min in Ar pressure of 800Torr, where the ingots are formed by pressing LaB6 powder at room temperature at a pressure of 0.4-0.5 GPa. The particles in LaB6 polycrystalline hardly bind; there are only a few pores at the joint parts of three particles and a few impurities exist in some pores. The sintering process for fabricating LaB6 polycrystalline is analysed and the formation of the pore and the impurities are studied from the point of surface tension.