A novel complex [ZnII3L2]6+ was designed and then synthesized by using subcomponent self-assembly of zinc trifluoromethanesulfonate (Zn(OTf)2), 2,4,6-tri(3-aminophenoxy) triazine, and 2-formylpyridine in CH3CN solution. The target compound's structure as a sandwich-like helicate was verified by 1H NMR and ESI-MS measurements, and the host-guest interactions between the complex and a number of guest molecules were investigated. It was discovered that the effect of the host-guest interaction significantly changed when the aldehyde component was replaced by 3-methylpyridine-2-carboxaldehyde, which suggested that the guest-binding sites may occur around the peripheral apertures of the complex. Also the binding behavior of the tetraphenylborate guests was further investigated, which quantified the host-guest stoichiometry in the ratio of 1:2.