Organic long-persistent luminescence (OLPL) materials are emerging as promising candidates for advanced applications in biomedical imaging, optoelectronics, and photonic devices. Despite their potential, achieving prolonged afterglow durations comparable to inorganic systems has remained a significant scientific challenge. Our research breakthrough addresses this limitation through innovative trace doping strategies, successfully extending OLPL afterglow durations to an unprecedented 7 hours.^[1] A key discovery is the "Sergeant and Soldier" effect, where strategic trace dopants fundamentally modify crystal packing, dramatically enhancing OLPL efficiency.^[2] Through comprehensive spectroscopic investigations, we uncovered that the performance enhancement originates from triplet-triplet energy transfer (TTET) mechanisms. Specifically, abundant triplet excitons within the host material drive sustained luminescence, a mechanism distinct from traditional intersystem crossing between guest and host molecules.^[3-4] Our insights provide a foundational understanding of energy transfer dynamics in room-temperature phosphorescence (RTP) and near-infrared (NIR) phosphors. By elucidating the intricate TTET mechanism, we offer a robust framework for rationally designing and tuning luminescent materials. These findings not only advance fundamental scientific knowledge but also unlock exciting possibilities for next-generation optoelectronic devices, innovative lighting technologies, and sophisticated biomedical imaging platforms.