This paper states the study on poling characteristic of cement-based piezoelectric ceramic composites. The experimental results are presented. The electromechanical coupling coefficient k is introduced to index the polarization behavior of composites under different poling conditions. A mechanism on molecular level is proposed to explain the macroscopically measured results and a first order model is developed to reveal the simple relationship between dipole domains and macroscopically measured parameters. And first order model is used to illuminate dependence of poling temperature and applied voltage on polarization procedure of composites. The model prediction is proved to consistent with the experimental results very well. © 2006 Elsevier B.V. All rights reserved.