Exploring an approach to control the nanostructures of pconjugated polymers has been an important research target in materials science, which has led to the creation of various functional materials with optimized p-electronic properties.[1] In particular, nanostructures of conjugated oligomer/ polymer blends have received growing interest in their applications, which include electronic devices such as fieldeffect transistors, light-emitting diodes, photovoltaic cells. [2] Several methods for controlling dimensionality, nanostructure, and morphology have been achieved through chemical and physical techniques that utilize microphase separation, layer-by-layer method, and so forth. [3, 4] Supramolecular approaches also have been applied for the alignment and organization of conjugated oligomers and polymers in a noncovalent manner, use of host matrix, liquid-crystalline phase, air-water interface, and so forth. [5, 6] From a supramolecular point of view, we recently proposed a new approach toward the alignment of conjugated polymers inspired by actin filament bundling proteins. A supramolecular cross-linking molecule ("aligner"), possessing conjugated polymer binding sites, bundles and aligns them in a noncovalent fashion. The concepts we have reported complement the existing techniques for supramolecular and macromolecular assembly. Introducing interactive sites for conjugated polymers at the spacial position of the aligner molecules allows control over the dimensions, morphologies, and interpolymer spacings. [7] This approach basically permits the construction of alternating arrays of different conjugated polymers, which depends upon the design of an aligner molecule displaying affinities toward such polymers.In this paper, we demonstrate that alternating arrays of amino-functionalized conjugated polymer (CP) and polyaniline emeraldine base (EB) were efficiently formed through the supramolecular bundling of a synthetic cross-linker 1 (Scheme 1). Very interestingly, the morphologies of the resultant conjugated polymer blends exhibited a well-regulated crystalline structure with periodicity of 2.0 nm. This approach can be regarded as a supramolecular two-dimensional polymerization of binary conjugated polymers. Compound 1 possesses two different binding sites which consist of cofacial porphyrinatozinc complexes and two palladium complexes. The former binding site was designed for recognizing CP and the latter for EB through coordination bonds. These binding sites are introduced around the terphenyl rotational axis so that one binding event would afford positive influence on the subsequent binding event. We wanted to integrate chromogenic groups so that we could confirm the binding events between 1 and the conjugated polymers in solution. When CP and EB are bundled and juxtaposed by 1, the distance between two polymers is calculated to be 2.0-2.3 nm in their energy-minimized states (see Supporting Information, Figure S2). Given the structures of the two different polymers, CP and EB, one can envision that an ideal ...