Chiral calix[4]arenes bearing long tertiary alkyl groups at the upper rim and S-1-phenylethylamine groups at the lower rim can form heat-set gels and egg-like vesicles enantioselectively with d-2,3-dibenzoyltartaric acid in cyclohexane, which is the first example of heat-set gels resulting from difference in interactions between two component gelators: in addition, the diameter of vesicles decreased with the increase in length of alkyl groups, which could be used to control the size of the vesicles.