novel optoelectronic technologies through the application of chemical and material science. [4-6] Owing to their advantages, such as facile molecular tailoring for property optimization, highly flexible adaptation, and low-cost fabrication, organic semiconductors based on polymers and small molecules containing π moieties are considered as great candidates for the essential elements of next-generation miniature consumer devices. [7-9] π-conjugated organic semiconductors have been successfully realized as a platform for various optoelectronic materials, owing to their unique light absorption, emission, and charge transfer characteristics. [10-12] Many studies have been devoted to improving the electrical and optical properties of organic semiconductors. Well-ordered assemblies based on π-conjugated polymers (CPs) and small molecules can resolve the limitations of carrier transport ability and performance stability that are common in amorphous organic materials. [13] Moreover, betterordered organic assemblies have proved to enhance optoelectronic performance owing to their high crystallinity, thereby minimizing the grain boundaries and decreasing the defect density. [14,15] There have been reviews on the assembly of organic semiconducting materials that expound on the basic principles of molecular design and selfassembly engineering, leading to the fabrication of functional nano/microstructures derived from various types of molecules. Furthermore, relevant applications on electrical, optical, and photoelectrical devices have also been demonstrated. [16-18] Notably, hybrid assembly has become an important aspect in the field of self-assembly. [19,20] Two or more types of organic semiconducting components are assembled into an ensemble through intermolecular interactions, such as van der Waals force, π-π stacking, and hydrogen bonding. [21,22] Hybrid assemblies can be classified into the following types: uniform-doped structures, [23-25] gradient-doped structures, [21] and hetero structures. [26-29] Most of these hybrid assemblies are utilized broadly as photonic elements, such as in light-emitting color barcodes, white light sources, optical wavelength converters, multiple optical channels, photoelectrical transducers, and chemical transducers. [19] Although these applications cover many aspects, only a few of them employ hybrid assemblies possessing biological functions. DNAs are generally regarded as carriers of genetic information. Nevertheless, pioneering studies, such as the study on DNA nano-architectures conducted by Seeman et al., have broadened our understanding of DNA molecules. [30,31] The outstanding Organic semiconductors are photonic and electronic materials with high luminescence, quantum efficiency, color tunability, and size-dependent optoelectronic properties. The self-assembly of organic molecules enables the establishment of a fabrication technique for organic micro-and nanoarchitectures with well-defined shapes, tunable sizes, and defect-free structures. DNAs, a class of biomacromolecules, have ...