Invoking efficient afterglow in metal-free organic molecules represents an important material advancement. However, organic afterglow suffers from low intensity and efficiency and generally needs to be excited by UV light owing to its spin-forbidden phosphorescent nature that essentially requires facile intersystem crossing (ISC). Here, we propose a strategy to bypass the traditional ISC through facilitating singlet-triplet transition to directly populate triplet excited states from the ground state by combining synergetic effects of both heavy/hetero-atom incorporation and aromatic aggregation. Verified by systematic experimental and computational investigations, this unique singlet-to-triplet absorption results in a much improved organic afterglow quantum efficiency up to 9.5% with a prolonged lifetime of 0.25 s under visible-light irradiation. Fundamentally, this work illustrates for the first time the great potential of the direct population method to red-shift the excitation wavelength and improve the afterglow efficiency, offering important clues for the development of triplet-state involved organic optoelectronic technologies.