The contributions of chain ends and branch points to surface segregation of long-branched chains in blends with linear chains have been studied using neutron reflectometry and surface-enhanced Raman spectroscopy for a series of novel, well-defined polystyrenes. A linear response theory accounting for the number and type of branch points and chain ends is consistent with surface excesses and composition profile decay lengths, and allows the first determination of branch point potentials. Surface excess is determined primarily by chain ends with branch points playing a secondary role.