This study presents a high-efficiency organic photovoltaic device based on self-organized discotic liquid crystals. The device uses a blend of hexa-perihexabenzocoronene (HBC-PhC₁₂) and perylene dye, which self-organizes into vertically segregated structures with a large interfacial area. This structure enables efficient photoinduced charge transfer between the perylene (electron acceptor) and HBC-PhC₁₂ (hole acceptor), leading to high external quantum efficiencies (EQEs) of over 34% near 490 nm and power efficiencies up to 2%. The high performance is attributed to the efficient charge transport through the vertically segregated perylene and HBC-PhC₁₂, as well as the large interfacial area between the donor and acceptor materials. The materials used are solution-processible conjugated organic materials that combine the electronic properties of semiconductors with the processibility of polymers. The HBC-PhC₁₂ is a discotic liquid crystal that forms columns of disc-shaped molecules, allowing quasi-1D transport of charge carriers and excitons. The perylene dye has high electron mobility and is used as an electron acceptor. The combination of these materials results in a highly ordered structure with a large interfacial area, which is essential for efficient charge separation and transport. The study demonstrates that complex structures can be engineered from novel materials using simple solution-processing steps. This approach enables the development of inexpensive, high-performance, thin-film photovoltaic technology. The results show that the self-organization of discotic liquid crystals can be used to create optimized structures for photoexciton dissociation and charge transport in solution-processed materials systems. This development brings together the simplicity of single-step solution processing with an efficient combination of molecular materials that can show unique ordering on intermolecular, mesoscopic, and interphase scales. The study also highlights the importance of intermolecular and mesoscopic ordering in achieving high performance in organic photovoltaics.This study presents a high-efficiency organic photovoltaic device based on self-organized discotic liquid crystals. The device uses a blend of hexa-perihexabenzocoronene (HBC-PhC₁₂) and perylene dye, which self-organizes into vertically segregated structures with a large interfacial area. This structure enables efficient photoinduced charge transfer between the perylene (electron acceptor) and HBC-PhC₁₂ (hole acceptor), leading to high external quantum efficiencies (EQEs) of over 34% near 490 nm and power efficiencies up to 2%. The high performance is attributed to the efficient charge transport through the vertically segregated perylene and HBC-PhC₁₂, as well as the large interfacial area between the donor and acceptor materials. The materials used are solution-processible conjugated organic materials that combine the electronic properties of semiconductors with the processibility of polymers. The HBC-PhC₁₂ is a discotic liquid crystal that forms columns of disc-shaped molecules, allowing quasi-1D transport of charge carriers and excitons. The perylene dye has high electron mobility and is used as an electron acceptor. The combination of these materials results in a highly ordered structure with a large interfacial area, which is essential for efficient charge separation and transport. The study demonstrates that complex structures can be engineered from novel materials using simple solution-processing steps. This approach enables the development of inexpensive, high-performance, thin-film photovoltaic technology. The results show that the self-organization of discotic liquid crystals can be used to create optimized structures for photoexciton dissociation and charge transport in solution-processed materials systems. This development brings together the simplicity of single-step solution processing with an efficient combination of molecular materials that can show unique ordering on intermolecular, mesoscopic, and interphase scales. The study also highlights the importance of intermolecular and mesoscopic ordering in achieving high performance in organic photovoltaics.