AbstractThe photophysics of dibenzo[a,j]phenazine (DBPHZ) in solution was investigated by steady‐state and time‐resolved spectroscopy. The nature of the solvent (methanol, acetonitrile, dichloromethane and cyclohexane were considered) only weakly affects the photophysical properties. The first excited singlet state features a lifetime of the order of 1 ns. Its fluorescence emission is centered around 420 nm and occurs with moderate yields of ≈0.1. The lowest triplet state is populated with yields of ≈0.3. Quantum chemical computations suggest that a state energetically close to the primarily excited singlet state is responsible for the efficient intersystem crossing towards the triplet manifold.