The performance and functionality of composites materials and devices composed of polymers are closely related to the quality of the interface between polymer and solid substance. Thus, it is of pivotal importance to obtain a better understanding of polymer behaviors at the solid interface. We here present how polymer chains adsorb onto a solid surface. We closely followed the trajectory of a single polymer chain on the surface as a function of temperature using atomic force microscopy. Combining the results with ones by a full-atomistic molecular dynamics simulation revealed that chains became more rigid on the way to reaching a pseudo-equilibrium state, accompanied by a change in their local conformations from mainly loops to trains. We also discuss the relaxation behavior of polymer chains in direct contact with a solid surface using interface-sensitive spectroscopy.