The volume from which a segment of a macromolecule in solution effectively excludes all other segments, i.e. those belonging to the same macromolecule as well as those belonging to other macromolecules. The excluded volume of a segment depends on the Gibbs and Helmholtz energies of mixing of solvent and polymer, i.e. on the thermodynamic quality of the solvent, and is not a measure of the geometrical volume of that segment.
Source:
Purple Book, 1st ed., p. 58 (http://old.iupac.org/publications/books/author/metanomski.html)