Water-soluble deoxy-azido cellulose derivatives were synthesized by heterogeneous carboxymethylation, applying 2-propanol/aqueous NaOH as slurry medium. The novel, carboxymethyl deoxy-azido cellulose provides a convenient starting material for the selective dendronization of cellulose via the copper-catalyzed Huisgen reaction yielding water-soluble carboxymethyl 6-deoxy-(1-N-[1,2,3-triazolo]-4-polyamidoamine) cellulose derivatives of first (degree of substitution, DS 0.51), second (DS 0.44) and third generation (DS 0.39). The novel biopolymer derivatives were characterized by FT-IR and NMR spectroscopy, intrinsic viscosity, sedimentation coefficient and weight average molar mass. Solution conformation and flexibility were estimated qualitatively using conformation zoning and quantitatively (persistence length) using the combined global method. Sedimentation conformation zoning showed a semi-flexible coil conformation and the global method applied to each carboxymethyl deoxy-azido cellulose and carboxymethyl 6-deoxy-(1-N-[1,2,3-triazolo]-4-polyamidoamine) cellulose derivative yielded persistence length all within the range of 2.8-4.0 nm with no evidence of any change in flexibility with dendronization.