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We performed cryogenic ion mobility-mass spectrometry (IM-MS) to study conformations of dibenzo-crown-ether complexes with Na+ and K+ ions at 86 K in the gas phase. Four dibenzo-crown-ethers (dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, and dibenzo-30-crown-1 with different cavity ring sizes were investigated. For dibenzo-18-crown-6 complexes with Na+ and K+, only one type of conformer was assigned by comparing the experimental collision cross sections with those predicted theoretically for candidate structures. In this