A novel biscalixarene with two kinds of calix[4]arene derivative units connected by four bridging chains, was facilely synthesized by “1 + 1” condensation mode in high yield. The element analyses, ESI-MS, 1H NMR and 1H– 1H COSY spectrum showed that the calix[4]arene units of compound 4 were in cone conformations and compound 4 possessed biscalixarene-tube structure.