An efficient path to prepare cellulose acetoacetates is reviewed in detail. The biopolymer dissolved in N , N -dimethylacetamide-LiCl is allowed to react with 2,2,6-trimethyl-4 H -1,3-dioxin-4-one at elevated temperatures without any catalyst. The procedure, which is briefly described in the literature (Marson and El Seoud in J Appl Polym Sci 74:1355–1360, 1999 ), utilizes simple to handle, commercially available compounds and requires only a short reaction time to obtain pure products that are promising starting materials for the design of advanced cellulose-based materials. Cellulose acetoacetates with degree of substitution of up to 1.84 can be obtained. A side reaction forming comb-like polymer structures was realized applying high molar ratio of cellulose to reagent (above 2 mol per mol) that was not known up to now. The hydrophobic cellulose acetoacetates can be transferred easily into nanoparticles with particle sizes ranging from 120 to 300 nm.