Taking poly (vinyl chloride) (PAH) as a template agent, (NH4)2CO3 as a precipitant, cerium carbonate crystals of special morphology were synthesized by using a liquid phase method. The morphology of cerium carbonate with different reaction time and structure of cerium carbonate crystals were characterized by the techniques of laser confocal microscope, scanning electron microscope, Fourier transform infrared spectroscopy and X-ray diffraction. The results show that under the action of PAH, the morphology of cerium carbonate was gradually transformed into hexagonal flake from initial rodlike, and this process was related with the orientation adsorption of PAH to the different crystal faces of cerium carbonate. Meanwhile, the electrostatic adsorption process of PAH and crystal faces of the cerium carbonate materials were also simulated by material studio software, thus revealing the formation mechanism of PAH template regulated cerium carbonate morphology.