The dependence of polyelectrolyte multilayer thickness on salt concentration, salt type, solvent quality, deposition time, and polymer concentration is evaluated. Polymers are deposited on spinning silicon wafers. For the strong polycation/polyanion pair studied, film thickness is approximately proportional to the number of layers and the salt concentration. The irreversibility of overall molecule adsorption is indicated by the lack of exchange of surface (radiolabeled) for solution polymer. The hydrophobic nature of the driving force for polymer sorption is illustrated by the choice of salt counterion or solvent. Analyzed within the framework of ion exchange, the net energy of ion pair formation is not high, at most a few kT. Salt, competing with polymer segments for the surface, permits localized rearrangements, in the mechanism proposed, excess polymer is accommodated within several layers, rather than in one layer of loops and tails. Steric barriers coupled with slow conformational changes are responsible for long-term polymer adsorption. Considering the disorder and interpenetration, multilayer buildup has much in common with solution phase or coprecipitated polyelectrolyte complexes. Surface hydrophobicity can be enhanced using fluorinated surfactants as counterions.