Complex formation of the important nitramines, RDX, HMX and TNAZ with alpha-, beta-, and gamma-cyclodextrins (CDs) was studied using ion-spray mass spectrometry (IS-MS). Complexations between beta-CD/TNAZ, beta-CD/RDX, gamma-CD/RDX, and gamma-CD/HMX were detected in the gas phase by this technique. Control experiments using alpha-CD and TNAZ did not lead to a detectable molecular association, which is in accord with the previously reported NMR data. In addition, none of the nitramines showed any complex formation with the non-cyclic sugar, maltohexose. The IS-MS results are in agreement with the previously reported conclusions from proton nuclear magnetic resonance spin-lattice relaxation time measurements.