Selectively dendronized cellulose at C-6 was synthesized homogeneously (in DMSO) and heterogeneously (in methanol) by the conversion of 6-azido-6-deoxy cellulose (degree of substitution, DS 0.75) with polyamidoamine (PAMAM) dendrons possessing an ethynyl focal moiety via the copper-catalyzed Huisgen reaction (click reaction) under mild conditions. First to third generation of PAMAM-triazolo cellulose derivatives with DS values of up to 0.69 could be prepared, which are soluble in organic solvents (DMSO, DMF) and in water. The novel biopolymer derivatives were characterized by elemental analysis, FTIR, and NMR spectroscopic methods, showing no impurities and no conversion at the secondary positions.