The authors studied the influence of the molecular weight of polyacrylic acid (PAA) and polyacrylamide (PAM), solution pH and ionic strength, and the background electrolyte type on adsorption and the thickness of polyelectrolyte adsorption layers formed on ZrO(2) surface. Carboxyl groups distributed along PAA and PAM chains were shown to be responsible for their interface conformation, which directly influences the thickness of the adsorbed polyelectrolyte layers. Bonding of macromolecules with solid surface occurs through the hydrogen bridges of these groups. Two methods were applied to determine the PAA and PAM adsorption layer thickness on ZrO(2), i.e., SAXS (small angle X-ray scattering) and viscometry. Despite some limitations of the SAXS method resulting from the relationship between the size of solid pores, polymer molecular weight, and conformation of the adsorbed macromolecule, all obtained SAXS results were very close to those calculated from viscometry data.