The salts Na[CF3SO2N(CH2)(3)OCR3] and K[CF3SO2N(CH2)(3)OCH3] form amorphous complexes with cryptand and crown ether macrocycles, which exhibit substantial ionic conductivity. The formation of an amorphous phase is thought to be favored by a mismatch between the cavity size of the macrocycle and the diameter of the cation. Complexes were examined by thermal, spectroscopic and conductivity methods to determine the role of the cation and the size mismatch with complexing macrocycles on ionic glass formation.