Surface properties of polymers are known to be of considerable importance in many applications such as coatings, moldings, adhesives, and fibers. Hydrophilic modification of non-polar polymers can be useful to improve wetting, adhesion, and antistatic properties; while hydrophobic modification of polar polymers can be useful to improve water and oil repellency and frictional properties. From the literature, the surface regions of polymer can reorient or restructure in response to the local micro-environment in order to minimize their interfacial free energy with the surrounding phase. These motions may be due to relaxation mechanisms in the surface region, perhaps due to surface-induced water plasticization at a polymer-water interface region. Such motions can be activated at or near room temperature. Understanding of the surface motions of a polymer are useful, especially in the area of the surface modification and surface coating of plastics. There are a variety of molecular motions present in synthetic polymers. For example, the rotation of a side chain about a carbon-carbon bond (beta relaxation or transition) is observed in acrylate and methacrylate polymers, which have ester-linked side chains. The side chain motions can be activated at room temperature, even though the glass transition temperature of the polymer is 110°C. This shows a possible way to study the behavior of a PMMA surface under different surroundings. Surface analysis experiments and results are described in this paper.