In this study, we presented a newly synthesized pyrene-naphthalene diimide(NDI)-pyrene triad. The optical and structural properties were examined using various characterization techniques. A donor-acceptor-donor triad molecule exhibited a strong charge transfer, though there existed neither intramolecular nor intermolecular hydrogen bonding sites, due to the formation of preferential complementary complex between pyrene and NDI. Powder XRD measurement revealed a sharp and distinctive X-ray patterns, indicating the presence of microcrystalline-like structure. POM images showed anisotropic fingerprint texture similar to that of cholesteric phase, and SEM images showed numerous columnar structures with length of 1 to 10μm. Above observation clearly demonstrated that π-complementary NDI-pyrene interactions in the traid was strong enough to form columnar aggregates in the long range.