Two crystals based on cucurbit[5]uril and cucurbit[7]uril, C30H30N20O10 center dot 2CF(3)SO(3)H center dot 7.25H(2)O (1) and C42H42N28O14 center dot CF3SO3H center dot 8H(2)O (2) have been synthesized in trifluoromethanesulfonic acid and structurally determined by single-crystal X-ray diffraction analyses. These two crystal structures demonstrated that the highly-ordered trifluoromethanesulfonate anions play essential roles in the formation of three-dimensional supramolecular frameworks with 1D elliptical channels or circular channels.