A new class of phosphole oxide based alkynylplatinum(II) 2,6-bis(N-alkylbenzimidazol-2'-yl)pyridine (bzimpy) complexes were synthesized and characterized. Their self-assembly was driven by hydrophobic-hydrophobic and π-π stacking interactions. The self-assembly properties were also investigated by UV/Vis absorption spectroscopy, which revealed that the alkyl-chain length of the bzimpy moiety and the π-surface area of the alkynyl ligand have significant influence on the overall self-assembly process. The alkyl-chain length also affected the morphological structures of the aggregates, which were studied by transmission electron microscopy and scanning electron microscopy.