Propargyl cellulose with regioselective functionalization pattern was synthesized by nucleophilic displacement reaction of 6-O-toluenesulfonyl ester of cellulose (degree of substitution, DS 0.58) with propargyl amine. The novel 6-deoxy-6-aminopropargyl cellulose provides an excellent starting material for the selective dendronization of cellulose at position 6 via the copper-catalyzed Huisgen reaction yielding 6-deoxy-6-amino-(4-methyl-[1,2,3-triazolo]-1-propyl-polyamido amine) cellulose derivatives of first- (DS 0.33) and second (DS 0.25) generation, which are soluble in polar aprotic solvents. The novel biopolymer derivatives were characterized by elemental analysis, FT-IR spectroscopy, and one- and two dimensional NMR spectroscopy, showing no side reactions (cross-linking) or impurities and no conversion at the secondary positions.