Driven by metal coordination, a flexible crown ether was self-assembled into neutral discrete complexes with two organoplatinum acceptors. Specifically, a [1 + 1]-assembled structure was separated from self-assemblies with different stoichiometries by vapor diffusion of acetone into their dichloromethane solution. The formation of these crown ether-incorporated self-assemblies was confirmed by NMR, elemental analysis, and X-ray single-crystal analysis.