A novel strapped porphyrin receptor Zn1, in which two electron-rich bis(p-phenylene)-34-crown ether-10 units are incorporated, has been designed and synthesized from the newly developed intermediate 7 for investigating new chemistry of molecular recognition. 1 H NMR and UV -Vis studies revealed that Zn1 displays relatively weak binding abilities to neutral electron deficient naphthalene-1,8,4,5tetracarboxydiimide (NDI) derivatives 13 (no simple complexing stoichiometry was observed), 19 (K a ΒΌ48(^5) M 21 ) and 30 (K a ΒΌ46(^5) M 21 ) in chloroform-d, strong binding ability to pyridine derivative 25, (K a ΒΌ1.5(^0.12)Β£10 3 M 21 ) in chloroform, moderately strong binding ability to tetracationic compound 35β’4PF 6 (K a ΒΌ475(^50) M 21 ) in acetone-d 6 , and very strong binding affinity to compound 22 (K a ΒΌ6.5(^0.7)Β£10 5 M 21 ), which consists of one pyridine and two NDI units, in chloroform. Remarkable cooperative effect of the intermolecular metal -ligand coordination and donor-acceptor interactions in complex Zn1β’22 was observed by comparing the complexing behaviors between Zn1 and the appropriately designed guests. Complex Zn1β’22 possesses an unique three-dimensional tri-site binding feature. For comparison, the complexing affinity of 1 toward compounds 13, 19, and 30 in chloroform-d and 35β’4PF 6 in acetone-d 6 has also been investigated and the binding patterns in different complexes were explored. The results demonstrate that strapped porphyrin derivatives are ideal precursors for constructing new generation of three-dimensional multi-site artificial receptors for molecular recognition and hostguest chemistry.