Self-assembled multilayers of a strong polyanion, poly(sodium 4-styrenesulfonate) (PSS), and a strong polycation, poly[(diallyl-dimethyl-ammoium chloride)-stat-(N-methyl-N-vinyl acetamide)] (P(DADMAC-stat-NMVA)), are fabricated on silicon substrates. This article addresses the effect of electrostatics versus ion specificity. Therefore, multilayer formation and growth are investigated its a function of the charge density of the polycation, the type of salt in the polyelectrolyte dipping solution, and its ionic strength. This study focuses on monovalent ions(Li+, Na+, K+, Cs+, Rb+, F-,Cl-, Br-, and ClO3-). Ellipsometry and X-ray reflectometry data indicate that anions have a significantly larger effect on the thickness of the multilayer, but contrary to other studies on ion-specific effects, the influence of the type creation is not negligible at higher salt concentrations. Larger ions, with smaller hydration shells, are highly polarizable and consequently interact strongly with charged polyelectrolytes, resulting in thicker and rougher multilayers. AFM Studies confirm a higher roughness of the multilayer prepared from larger anions. The substrate can mask ion-specific effects over a distance of about 10 nm. Ion-specific effects become important above an ionic strength of 0.1 M in the case of anions and above an ionic strength of 0.25 M for cations. At lower ionic strengths, electrostatic interactions between and within the polyelectrolyte chains are dominating. Reducing the degree of polymer charge down to 75% does not shift this threshold of ionic strength. It is shown that a combination of ionic strength, polymer charge, and type of ion is a suitable tool for inning the mobility and stability of polyelectrolyte multilayers.