X-ray photoelectron spectroscopy (XPS) was employed to quantify adsorption of polyelectrolytes from aqueous solutions of low ionic strength onto mica, glass, and silica. Silica surfaces were conditioned in base or in acid media as last pre-treatment step (silica-base last or silica-acid last, respectively). Consistency in the determined adsorbed amount, Γ, was obtained independent of the choice of XPS mode and with the two quantification approaches used in the data evaluation. Under the same adsorption conditions, the adsorbed amount, Γ, varied as Γmica > Γsilica-base last ≈ Γglass > Γsilica-acid last. In addition, the adsorbed amount increased with decreasing polyelectrolyte charge density (100% to 1% of segments being charged) for all substrates. Large adsorbed amount was measured for low-charge density polyelectrolytes, but the number of charged segments per square nanometer was low due to steric repulsion between polyelectrolyte chains that limited the adsorption. The adsorbed amount of highly charged polyelectrolytes was controlled by electrostatic interactions and thus limited to that needed to neutralize the substrate surface charge density. For silica, the adsorbed amount depended on the cleaning method, suggesting that this process influenced surface concentration and fraction of different silanol groups. Our results demonstrate that for silica, a higher density and/or more acidic silanol groups are formed using base, rather than acid, treatment in the last step. © 2022 The Authors.