Cellulose acetoacetates with and without other ester groups were prepared directly from cellulose by reaction with diketene or tert-butyl acetoacetate (and, where appropriate, a carboxylic anhydride) in N,N-dimethylacetamide (DMAC)/LiCl or 1-methyl-2-pyrrolidinone (NMP)/LiCl solution. This is the only method yet described for the direct synthesis of these polymers from cellulose and, except for the triester, the only method available for synthesis of cellulose acetoacetates which do not contain another ester group. The products span the entire degree of substitution (DS) range, are amorphous, and are readily soluble in various solvents depending on DS. Cellulose acetoacetates of low DS are soluble in water. Some of these water-soluble materials can be formulated into cross-linkable coatings which have outstanding solvent resistance. Methods have been developed for the determination of DS by proton NMR spectroscopy. Proton and carbon-13 NMR resonance assignments for cellulose tris(acetoacetate) are also provided.