Two newly identified supramolecule structures arise from self-assembly of theCalix[4]arenes derivatives 1 and 2: one ethyl ester of 1 (or 2) enters into the cavity of another 1 (or 2) forming a 1D long chain structure. The interaction force of the molecules and the crystallization energy might be an important driving force for forming theself-assembled calix[4]arene.