Organic long-persistent phosphorescent materials are advantageous due to the cost-effectiveness and easy processability. The organic phosphorescence is achieved by the long-lived triplet excitons, and the challenges are recognized regarding the various nonradiative pathways to quench the emission lifetime. Taming long-lived phosphorescence is generally engaged with the charge-transfer or exciton diffusion in molecular stacking to stabilize triplet excitons or form a photoinduced ionized state.