The relationships between (meth)acrylate polymers structure and its film surface wettability were analyzed. A series of random (meth)acrylate polymers were prepared by the free radical solution polymerization and their coating film wettability was analyzed by measuring water contact angles(CAs). There are three kinds of functional groups on the surface, including methyl, ethyl and ester group, and the surface energy of ester group is greater than the others. The more ester group on the surface will result in the better surface hydrophilicity. Polymer structure parameters as the side chain length(m) and glass temperature(Tg) are taken into account in discussing the migration of functional group to the outermost surface. It was found that the less m and lower Tg will promote the motion of the side chain and hence cause the surface exhibiting more hydrophilicity.