In this article, pollucite ceramic with high relative density and low coefficient of thermal expansion (CTE) was prepared from Cs-based geopolymer using synthetic metakaolin. Crystallization and sintering behavior of the Cs-based geopolymer together with thermal expansion behavior of the resulted pollucite ceramic were investigated. On heating at 1200 degrees C for 2 h, the amorphous Cs-based geopolymer completely crystallized into pollucite based on crystal nucleation and growth mechanism. Selected area diffraction analysis and XRD results confirmed the resulted pollucite ceramic at room temperature was pseudo-cubic phase with superlattice structure. Compared with Cs-based geopolymer using natural metakaolin, geopolymer using synthetic metakaolin in this article showed a much lower viscous sintering temperature range, which started at 800 degrees C, reached a maximum value of -7.47 x 10(-4) /degrees C at 1121.9 degrees C, and ended at 1200 degrees C. Cesium volatilization appeared only when temperature was above 1250 degrees C. Therefore, densified pollucite ceramic can be prepared from Cs-based geopolymer using synthetic metakaolin without cesium volatilization. Abnormal thermal shrinkage of pollucite ceramic was observed at temperature range from 25.3 to 54.6 degrees C because of pseudo-cubic to cubic phase transition, and its average CTE was 2.8 x 10(-6)/degrees C from 25 to 1200 degrees C.