The characters of hydrogen-bond of 2,2’-bi-1H-imidazole (H2BIM) system were examined from a viewpoint of the proton-transfer (PT) and electron-transfer (CT) interactions. To make the effects of the dibenzo substitution of H2BIM molecule clear, we prepared the charge-transfer complexes of dibenzo-2,2’-bi-1H-imidazole (H2BBIM) and H2BIM systems with 7,7,8,8-tetracyanoquinodimethane (TCNQ). The one-dimensional column of TCNQ was confirmed by the crystal structural analysis, however, the packing forms of the H2BIM and H2BBIM systems were entirely different to each other. The H2BBIM system in the TCNQ complex formed the one-dimensional column which is parallel to the TCNQ stack, while the H2BIM system was constructed by the hydrogen-bonded dimer unit along the perpendicular direction to the TCNQ column.