Abstract Mass spectral fragmentation processes and pathways of a series of nitro, dinitro and trinitro derivatives of naphthalene have been studied. Collision‐induced dissociation mass spectra were obtained using a tandem BB mass spectrometer. Major fragmentation pathways included loss of NO 2 from the molecular ion, followed by loss of NO and/or CO. Additional fragmentations included loss of OH from the molecular ion ion some of the compounds investigated.