Metal-free organic phosphorescent materials have attracted considerable attention in the fields of organic electronics and bioelectronics. However, it remains a great challenge to achieve organic phosphors with high quantum efficiency in a single-component system. We designed and synthesized two organic phosphors (PDCz and PDBCz) with an ultralong organic phosphorescence (UOP) feature. Both molecules showed ultralong emission lifetime of >200 ms. For PDBCz crystal, it was found that the absolute phosphorescence quantum efficiency reaches up to 38.1%. Combining the experimental and theoretical studies, the highly efficient UOP was mainly attributed to the intramolecular space heavy-metal effect, which facilitates the spin-orbit coupling between singlet and triplet excited states to effectively promote the intersystem crossing. This study will provide a new platform to rationally design highly efficient UOP materials and show its potential in the field of flexible electronics.