For the first time, we show the presence of nitro substituted naphthalenes in both mainstream and sidestream tobacco smoke using electron monochromator-mass spectrometry. Only one mainstream smoke sample showed the presence of 1-nitronaphthalene (1-NN) at 20 pg/cigarette, while all of the sidestream smoke samples showed the presence of 1-NN at levels ranging from 0.40 to 0.60 ng/cigarette and 2-NN at quantities ranging from 1 to 2 ng/cigarette. Additionally, these levels showed a ratio of ~1:3 for 1-NN to 2-NN which demonstrates that the formation of 2-NN is favored under sidestream combustion conditions. No larger ring structure (>2) nitro-aromatics were identified.