Multiflorumisides A-G (1-7), seven new dimeric stilbene glucosides with two rare coupling patterns, were isolated from the roots of Polygonum multiflorum. The structures of these new dimeric stilbene glucosides were elucidated through comprehensive spectroscopic and chemical analyses. The absolute configurations of 3 and 5-7 were established by comparing their experimental and quantum-chemical ECD data. Putative biosynthetic pathways toward the dimers and their suppressive effects against nitric oxide production in lipopolysaccharide-stimulated RAW264.7 cells are also discussed.