Polymeric articles, including membranes, with surfaces having a desired chemical functionality are created by surface segregation of a branched component blended with a compatible, matrix base component, the branched component having the desired chemical functionality. In particular, hydrophilic surfaces are created via surface segregation of a branched hydrophilic copolymer blended into a polymer matrix. The use of branched molecular architecture provides a thermodynamic mechanism for the segregation of the hydrophilic species to the surface and a means for achieving a high surface coverage of the hydrophilic moiety. The branched hydrophilic copolymer can be defined by a random copolymer including two or more methacrylate or acrylate monomers, at least one of which features a short hydrophilic side chain, such as a polyethylene glycol side chain. The branched hydrophilic copolymer is compatible, and well-entangled, with the acrylate polymer matrix.