Metal-free dual singlet–triplet organic light-emitting diode (OLED) emitters can provide direct insight into spin statistics, spin correlations and spin relaxation phenomena, through a comparison of fluorescence to phosphorescence intensity. Remarkably, such materials can also function at room temperature, exhibiting phosphorescence lifetimes of several milliseconds. Using electroluminescence, quantum chemistry, and electron paramagnetic resonance spectroscopy, we investigate the effect of the conjugation pathway on radiative and nonradiative relaxation of the triplet state in phenazine-based compounds and demonstrate that the contribution of the phenazine nπ* excited state is crucial to enabling phosphorescence.