Photochemical afterglow materials have drawn considerable attention due to their attractive luminescent properties and great application potential. Considering the classical photochemical afterglow materials always exhibit poor luminescence, it is urgent to gain fundamental understanding of the main limiting factors. Here, we identified the existence of a dark-state triplet in the photochemical process, and an overwhelming percentage of ~98.5% was revealed for this non-emissive triplet state. Guided by these observations, we proposed to activate an unprecedented triplet energy transfer relay to simultaneously harness the singlet and triplet energy. Consequently, an upconverted afterglow material was constructed with amazing luminescence performance albeit its moderate fluorescence emission property. The generality of this strategy was evidenced by the adaptation to similar emitters with varied emission wavelengths. The optimized afterglow performance enabled time-gated upconversion bioimaging under ultralow-power excitation. This study not only reveals the energy transfer pathways for photochemical afterglow but also paves the way for rational design of bright upconverted materials with ultralong lifetime.