Pyrolysis ammonia chemical ionization (PyCI) mass spectrometry was performed on hydroxyethyl-, hydroxypropyl-, methyl-, hydroxypropylmethyl-, and ethylhydroxyethyl celluloses. The mass peaks in the PyCI mass spectra of these cellulose ethers could be assigned to the ions of pyrolytic dissociation products which form via the [2 + 2 + 2] cycloreversion and the Ei, elimination pyrolysis pathway. Structural information about the residual amount of nonderivatized cellulose, the relative chain length distributions of the substituents in hydroxyalkyl celluloses, and the end-capping of hydroxyalkyl substituents by alkyl groups in the mixed cellulose ethers is obtained. Interference of secondary pyrolysis products in the PyCI mass spectra is found to be of minor importance, especially in the lower mass regions.