Staudinger reactions are frequently highly chemoselective and can occur under very mild conditions, so are attractive methods for efficient functionalization of polysaccharides. This review describes recent investigations that exploit Staudinger-related reactions to effectively alter physical and chemical properties of polysaccharides in order to make them more diversely applicable. Staudinger-related reactions, such as Staudinger reduction, Staudinger ligation, and traceless Staudinger ligation comprise a powerful family of techniques enabling preparation of a wide range of polysaccharide derivatives with excellent chemoselectivity and the potential for excellent regioselectivity when combined with other methods. The remarkably mild conditions of the Staudinger reactions, combined with the abiotic nature of the azide group, make these reactions exceptionally attractive for modification of intact biological entities, including living cells.