Room temperature phosphorescence materials offer great opportunities for applications in optoelectronics, due to their unique photophysical characteristics. However, purely organic emitters that can realize distinct electrophosphorescence are rarely exploited. Herein a new approach for designing heavy-atom-free organic room temperature phosphorescence emitters for organic light-emitting diodes is presented. The subtle tuning of the energy diagrams of singlet and triplet excited states by appropriate choice of host matrix allows tailored emission properties and switching of emission channels between thermally activated delayed fluorescence and room temperature phosphorescence. Moreover, an efficient and heavy-atom-free room temperature phosphorescence organic light-emitting diodes using the developed emitter is realized.