In this work, we investigate a multicomponent synthetic method for combining saccharides with cellulose to produce saccharide branched cellulose (b-Cel). First, cellulose is modified conventionally using carboxymethyl to create carboxyl functional groups for multicomponent reactions. The Passerini three-component reaction (Passerini-3CR) is then used to synthesize the saccharide b-Cel, with particular attention paid to the scope of the substrate and reaction process optimization. The structure of saccharide b-Cel is regulated by modifying the carboxyl group of cellulose molecules, the kind of saccharide molecules (including glucose, galactose, lactose, cellobiose, and cellulose), and the degree of branching. The branched structure of saccharide b-Cel greatly influenced its rheological characteristics and solubility. This work presents a practical method for the synthesis of artificial branching polysaccharides and is crucial for the development of innovative materials based on biomass.