Fourier transform relaxation NMR has been used to study how the mobility of poly(ethylene oxide) is affected by its adsorption onto colloidal silica particles of various sizes. Novel results have been obtained which illustrate the unexploited potential of this method for the Study of interfacial species in complex systems. The results quantify how polymer mobility varies along an adsorption isotherm. When the particles are in excess, the polymer is strongly adsorbed and hence has a large spin-spin magnetic relaxation rate constant, R-2. The value of R-2 in this region increases with particle size, because the associated reduction in particle surface curvature results in a reduction in the mobility of the adsorbed polymer. This is accompanied by a reduction in the signal intensity, as a higher fraction of the polymer is adsorbed in the form of train segments too immobile to detect using the Carr-Purcell-Meiboom-Gill pulse sequence. When the polymer concentration reaches similar to 0.5 mg m(-2), the initial region of high affinity adsorption ends and so the polymer solution concentration increases. This is accompanied by a reduction in R-2, which then approaches the value for a simple polymer solution in the absence of particles. The results are corroborated by comparison with rheological Measurements and molecular dynamics simulations of an analogous particle-polymer system.