The particle/polymer/solvent suspension system shows complicated microstructure. When the suspension system experiences an industrial process such as coating and drying, the system experiences microstructural change. In this study, we investigated the microstructural change during the drying of a silica/polyvinyl alcohol (PVA) suspension, with an emphasis on suspension stability. We controlled the amount of PVA adsorption on the silica surface by adjusting the pH (1.5, 3.6, and 9) of the silica/PVA suspension. The amount of adsorption was measured to increase with decreasing pH, and the degree of flocculation in the silica/PVA suspension became stronger with decreasing pH. However, through the measurement of stress development during drying and the observation of film microstructure after drying, we found that the more strongly flocculated suspension became a more disperse, close-packed film after drying. By evaluating the potential energy, we could suggest the role of adsorbed polymers in structural change during the drying of the silica/PVA suspension. As pH decreases, the adsorbed polymers could bridge the particles and lead to a flocculated suspension before drying. As the solvent evaporates during drying, the adsorbed polymers introduce steric repulsion between approaching particles, leading to a change from flocculated to dispersed microstructure. This implies that the required silica/PVA film performance and the microstructure of the silica/PVA suspension can be tailored through controlling the polymer adsorption in suspension.