The control of the emission properties of doping materials through molecular design makes organic materials potentially promising candidates for many optoelectronic applications and devices. However, organic doping systems with high quantum yields and persistent luminescence processes have rarely been reported, and their luminescence mechanisms are still not well established. Here we developed a series of purely organic heavy-atom-free doping systems. The guest molecules can dope either donor or acceptor matrixes, both leading to an enhanced fluorescence (Φ = 63-76%) and room-temperature phosphorescence (Φ = 7.6-14.5%, τ = 119-317 ms) under ambient conditions. XRD measurements and density functional calculations results indicated ultralong phosphorescence was determined by both the cocrystalline state and the energy levels between the host and guest materials. The doping materials are fairly stable to light, heat, and humidity. This work may provide unique insight for designing doping systems and expanding the scope of organic phosphorescence applications.