The guest- or solvent-induced assembly of a tetracarboxyl-cavitand 1 and a tetra(3-pyridyl)-cavitand 2 into a heterodimeric capsule 1(.)2 in a rim-to-rim fashion via four intermolecular CO2H...N hydrogen bonds has been investigated both in solution and in the solid state. In the H-1 NMR study, a 1:1 mixture of 1a and 2a (R = (CH2)(6)CH3) in CDCl3 gave a mixture of various complicated aggregates, whereas this mixture in CDCl2CDCl2 or p-xylene-d(10) exclusively produced the heterodimeric capsule 1a(.)2a. It was found that an appropriate 1,4-disubstituted-benzene is a suitable guest for inducing the exclusive formation of 1a(.)2a in CDCl3. The ability of a guest to induce the formation of guest-encapsulating heterodimeric capsule, guest@(1a(.)2a), increased in the order p-ethyltoluene < 1-ethyl-4-methoxybenzene less than or equal to 1-ethyl-4-iodobenzene less than or equal to 1,4-dibromobenzene < 1-iodo-4-methoxybenzene less than or equal to 1,4-dimethoxybenzene less than or equal to 1,4-diiodobenzene. The H-1 NMR study revealed that a CH-halogen interaction between the inner protons of the methylene-bridge rims (-O-HoutCHin-O-) of the 1a and 2a units and the halogen atoms of 1,4-dihalobenzenes and a CH-pi interaction between the methoxy protons of 1,4-dimethoxybenzene and the aromatic cavities of the 1 a and 2a units play important roles in the formation of 1,4-dihalobenzene @ (1a(.)2a) and 1,4-dimethoxybenzene @ (1a(.)2a), respectively. A preliminary single-crystal X-ray diffraction analysis of guest @ (1b(.)2b) (R = (CH2)(2)-Ph; guest = 1-iodo-4-methoxybenzene or p-xylene) confirmed that the guest encapsulated in 1b(.)2b is oriented with the long axis of the guest along the long axis of 1b(.)2b and that the iodo and the methoxy groups of the encapsulated 1-iodo-4-methoxybenzene are specifically oriented with respect to the cavities of the 2b and 1b units, respectively.