Pectin is a group of carbohydrate polymers constructing the primary cell walls and the middle lamella of terrestrial plants. Herein, we demonstrated the structure and immunomodulatory activity of the major pectic polysaccharide DL-3B(2) isolated from the leaves of Diospyros kaki. Based on composition analysis, methylation analysis, two-step acid hydrolysis, lithium-mediated selective degradation, (13)C NMR spectroscopy, and electrospray ionization mass spectrometry, DL-3B(2) was found to contain an alpha-1, 4-linked galacturonic acid (GalA) backbone with some insertions of alpha-1, 2-linked rhamnose residues. The arabinan- and arabinogalactan-side chains were attached to O-4 of the rhamnose residues, whereas the linear arabinoxylan was probably linked to O-3 of the GalA residues. Immunological tests in vitro showed that DL-3B(2) could help stimulate lipopolysaccharide-induced B lymphocyte proliferation, but not ConA-induced T lymphocyte proliferation, and that the arabinose residues play a role in maintaining this immunological activity.