Gas-phase ion chemistry is a useful approach for the investigation of physical organic chemistry and the study of reactivity, structure, and thermochemical properties of ionic and neutral organic substrates. Herein, one-step dehydration of gas-phase benzyl amine alcohols to give benzazetidines was discovered without the use of catalysts. Mechanistic investigations of the gas-phase dehydration reactions were explored to study the possible influence of charged microdroplet acceleration during electrospray ionization (ESI) and collisions occurring during ion transfer through the atmospheric pressure interface (API) of the mass spectrometer. The product ion distribution was observed to be less sensitive to droplet effects (spray distance and voltage), and temperature of transfer capillary in the API. However, the product ion distribution exhibit high sensitivity to different S-lens radio frequency (RF) voltage of the API, providing evidence that the dehydration reaction is driven by collisions during ion transfer in the API. With this insight, we developed atmospheric pressure thermal dissociation platform that allowed thermal-induced collisions outside of the mass spectrometer when the benzyl amine alcohols are carried through a heated coiled tube. Up to 98% dissociation efficiency was achieved with the coiled tube heated to a temperature of 200 °C, yielding only the desired benzazetidine product. By performing the atmospheric pressure thermal dissociation experiment outside of the mass spectrometer, we believe it will be straightforward to collect the dehydration product.