Nuclear magnetic resonance spectroscopy is used to probe the conformation and the dynamics of a macromolecular chain near a solid surface of the interface polymers grafted on silica. NMR of ¹³C, ¹H and ²H nuclei of grafted polymer chains permits to investigate the behaviour (conformation, mobility etc.) of polymers at the interface without introducing probe and to give access to the statistical organization of polymers at the interface. Utilisation of different techniques such as “Pseudo Solid Echo” sequences, “Magic Angle Spinning” with variable temperature, observation of the relaxation function of different nuclei (¹H, ²H, ¹³C) and “Cross Polarisation” (¹H-¹³C) allow to propose a methodology of approach. The example chosen for illustration is poly(ethylene) oxide grafted on silica. For grafted polymers, the dipolar interaction is an important factor in the relaxation process. This interaction, which depends on the local concentration of monomer-units, allows an original approach to polymer motion and conformation of polymers at the interface. Using NMR technique, we have shown the possibility of proposing some schematic representations of conformation of polymers at the interface and suggesting different models for the surface layer for the two extreme grafting levels. NMR appears to be a powerful, sensitive and versatile method for probing the structure and organisation of a polymer layer attached to a solid surface at the molecular level.