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, π–π stacking interaction, S⋯H–C interaction and S–π interaction were recognized between base and adjoining thiacalix[4]arene stacking.