A model is proposed for the formation of the microstructure in polymer-modified cementitious materials. Cement hydration and polymer film formation were studied, with specific emphasis on the synergetic effect between cement particles and polymer particles. Alterations at the microstructure level result in macroscopic changes in the properties of the modified material. In this paper, the influence of the polymer addition on the appearance of the cement hydrates and the presence of the polymer film through the cement hydrates are presented in relation to the minimum film forming temperature. Owing to the presence of the cement particles and to cement hydration, film formation can take place at lower temperatures, so that a polymer dispersion with a slightly higher MFT (minimum film forming temperature) can be used. This is important for the physical and mechanical properties of the polymer-modified materials. The findings have been included in an integrated model based on the three-step model of Ohama, in which the polymer film formation and the cement hydration processes are integrated in relation to each other. A time-dependent evaluation of both processes was incorporated. The research presented in this paper was part of a PhD research at the Civil Engineering Department, University of Leuven, Belgium [1].