The adsorption, adsorption layer structure, and molecular mobility in thermodynamically different systems (miscible polycarbonate (PC)-poly-epsilon-caprolactone (PCL)-chloroform (CHCl3) and immiscible polystyrene (PS)-poly(butyl methacrylate) (PBMA)-carbon tetrachloride (CCl4)) have been studied using high resolution NMR spectroscopy. It was found that the molecular mobility of nonadsorbing polymer in a definite concentration range was restricted for both systems investigated. In the thermodynamically immiscible system PS is not adsorbed on the solid surface, but the mobility of PS segments is restricted due to their topological entanglement with the adsorbed PBMA macromolecules and aggregates. As distinct from immiscible pairs, in a miscible system, in addition to the topological interaction between PS aggregates and macromolecules and PCL macromolecules, one should take into account the formation of the common aggregates for both polymers at concentrations above C*. Adsorption of these aggregates causes restriction in the molecular mobility of both polymers.