An intriguing supramolecular tetrahedral aggregate [Cu4I(ptt)(3)(Hptt)(3)](4) (1; Hptt = 1-phenyl-1H-tetrazole-5-thiol) based on novel copper(I) iodide thiolate clusters in the solid state has been synthesized and characterized. Four tetra-copper(I) cluster molecules join together with the cooperation of multiple offset face-to-face pi-pi stacking (OFF) and edge-to-face C-H center dot center dot center dot pi (EF) interactions in the form of aryl embrace of a (EF)(3)(OFF)(3) motif, which leads to the formation of this tetrahedral aggregate. Furthermore, this complex exhibits a temperature-dependent green photoluminescence.