When an enzymatic reaction is performed in a reaction mixture containing cyclodextrin and a branched maltooligosaccharide or a saccharide mixture of the same in the presence of a branch-splitting enzyme such as pullulanase, a twig branched cyclodextrin, i.e. a branched cyclodextrin of which the branched portion is formed of a moiety of a branched maltooligosaccharide, is formed. This product is a novel compound not known in the prior art and is a useful material in various industrial fields such as foods, cosmetics, medicines and the like by virtue of the unique properties of, for example, clathrate formation and complex formation with atoms or ions of metals.