The generation of hexameric channels by self assembly of 5,11,17,23-tetrabromo-25,26,27,28-tetrapropoxythiacalix[4] arene (1) was successfully performed. The structure of the hexameric assembly (2) was provided by single crystal X-ray analysis, in which hydrogen bonding, pi-pi stacking interaction, S center dot center dot center dot H-C interaction and S-pi interaction were recognized between base and adjoining thiacalix[4]arene stacking.