The article discusses the development of high-efficiency organic photovoltaic devices using self-organized discotic liquid crystals (LCs) and crystalline-conjugated materials. The authors used hexa-peri-hexabenzocoronene (HBC-Phe12), a discotic LC, combined with a perylene dye to create thin films with vertically segregated perylene and hexabenzocoronene layers, maximizing the interfacial surface area. These films exhibit photovoltaic response with external quantum efficiencies (EQEs) exceeding 34% near 490 nm, attributed to efficient photoinduced charge transfer and effective charge transport through the segregated π systems. The solution-processed approach offers a simple, low-cost method to engineer complex structures, potentially enabling commercial applications in optoelectronic technologies. The study highlights the importance of intermolecular and mesoscopic ordering in achieving high performance in organic photovoltaics.The article discusses the development of high-efficiency organic photovoltaic devices using self-organized discotic liquid crystals (LCs) and crystalline-conjugated materials. The authors used hexa-peri-hexabenzocoronene (HBC-Phe12), a discotic LC, combined with a perylene dye to create thin films with vertically segregated perylene and hexabenzocoronene layers, maximizing the interfacial surface area. These films exhibit photovoltaic response with external quantum efficiencies (EQEs) exceeding 34% near 490 nm, attributed to efficient photoinduced charge transfer and effective charge transport through the segregated π systems. The solution-processed approach offers a simple, low-cost method to engineer complex structures, potentially enabling commercial applications in optoelectronic technologies. The study highlights the importance of intermolecular and mesoscopic ordering in achieving high performance in organic photovoltaics.