The stability of thin water films on silicon substrates coated with cationic and anionic polyelectrolytes was investigated by the thin film pressure balance technique. Depending on the surface charge of the substrate, the water films are either stable (on negatively charged wafers) or rupture rapidly (on positively charged wafers). It is supposed that this behavior is due to a negative surface charge of the free water surface. The underlying assumption that the films' stability is due to electrostatic interactions is supported by measurements of the disjoining pressure on silicon wafers with a native oxide layer, which indicates a decrease of the film thickness, and thus decreasing repulsive interaction between the two film interfaces, with increasing ionic strength.