The performance of a polymer composite material, in which inorganic fillers are dispersed, is closely related to the aggregation states and dynamics of polymer chains at the interface with the filler. In this short review, we first introduce the relaxation behavior of polymer chains in thin films supported on solid substrates, suggesting that the surface and interfacial dynamics are faster and slower than that in the bulk. Then, aggregation states and dynamics of rubbery chains as well as glassy ones are directly discussed on the basis of the interfacial sensitive vibrational spectroscopy. We clearly demonstrate that chains at the substrate interface can be hardly relaxed even at a temperature being far above the bulk glass transition temperature. Finally, we try to combine this knowledge with the viscoelastic properties of bulk composite materials composed of a rubbery polymer and an inorganic filler.