In this paper, we have built up the organic-inorganic hybrid co-crystal (1) by using the derivative of ethylenediammonium cations (N,N,N′,N′-tetra-p-methoxybenzyl-ethylenediamine, L1) and [CuCl4]2−anions. The reaction was carried out by mixing MeOH solution of CuCl2·2H2O and HCl/MeOH solution of L1at room temperature. Two types of inclusion compounds can be formed when using different guest molecules. When guest molecules, such as anthracene or phenanthrene, were included, it resulted in the formation of interlayered structures: anthracene ⊂ [H2L1]2+·[CuCl4]2−(2) and phenanthrene ⊂ [H2L1]2+·[CuCl4]2−(3). When β-naphthyl phenol were included, it led to the formation of pillared-layered complexes of [1-chloride-β-naphthyl phenol]1.0·[β-naphthyl phenol]0.5·[methanol]1.0⊂ 2[H2L1]2+·2Cl−·[CuCl4]2−(4). [ABSTRACT FROM AUTHOR]