The influence of polyvinyl alcohol (PVA) and polyacrylamide (PAM) on the stability of acidic colloidal silica in aqueous environment was examined. Experiments were carried out on the original colloidal silica (CS), PVA modification and PAM modification. PVA- and PAM-modified CS could remain stable for 20 and 13 days in the oven under 50 °C; however, nonmodified CS is only stable for 9 days. The thermal stability of CS was significantly improved through PVA modification. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that the modified particles reveal better dispersibility. The action mechanism between polymer and CS was studied by particle size distribution, zeta potential, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR). The results show that the modified silica particles acquire more negative charge and the interactions among silica particles and PVA are stronger than among silica particles and PAM. Such differences appeared to be due to the loss of water molecules between C–OH of PVA and Si–OH bonds, which form a dense monomolecular adsorbed layer on the surface of the silica particles, thus increasing space steric repulsion. However, for the situation of PAM, the interaction was weakened. The results provided important basis to optimize stability of acidic CS in the aqueous environment.