We report a simple yet versatile solution route for constructing heterojunctions from luminescent organic charge-transfer (CT) complexes through a two-step seeded-growth method. Using this method, we achieved anisotropic and selective growth of anthracene-1,2,4,5-tetracyanobenzene (TCNB) complexes onto the tips of naphthalene-TCNB microtubes, resulting in the formation of microdumbbells. Significantly, the two-component microdumbbells appear as dual-color-emitting heterojunctions arising from integration of two distinct color-emitting materials. We further elucidated the two-step seeded-growth mechanism of the dumbbell-like organic heterostructures on the basis of structural analysis of the two crystals and surface-interface energy balance. In principle, the present synthetic route may be used to fabricate a wide range of sophisticated dual- or multicolor-emitting organic heterostructures via judicious choice of the CT complexes.