The self-assembly of supramolecular compounds based on organometallic compounds as building blocks has recently become one interesting research area in supramolecular chemistry. In this review, we focus on those containing six main-group heavy p-block metals (In, Tl, Sn, Pb, Sb, Bi), and illustrate how they are assembled into unusual supramolecular structures via weak interactions, especially secondary bonding and pi interactions.