The thermal degradation products of 1-alkyl-3-methyl-imidazolium-type ionic liquids (e.g., BMIM, EMIM), which are commonly used in cellulose chemistry, were identified. Imidazole (5), N-methylimidazole (6), and N-alkylimidazoles (7, 8) are the main products. Moreover, dimeric substituted imidazoles (9–11) were found carrying a methylene bridge formed from the N-methyl structure. The former 1-alkyl group (butyl or ethyl) was not present in any of the dimeric compounds. The N-methylene intermediate (12) acts as a precursor for the substituted imidazoles linked by a methylene group. All thermal degradation products are bases and catalyze the previously described reaction between the reducing end of celluloses and 1-alkyl-3-imidazolium cations. To minimize this side reaction, ionic liquids have to be liberated from such basic compounds prior to application as cellulose solvents. In this regard, the usage of “recycled” (and unpurified) ionic liquids has to be treated with caution.