At high brightness, triplet–triplet annihilation (TTA) reduces the efficiency of organic light-emitting diodes. Triplet diffusion may considerably enhance this effect, which is otherwise limited by the rate of long-range interactions. Although its role can be clarified by studying the emissive dye concentration dependence of the TTA loss, we demonstrate here the practical applicability of a more direct method, requiring a study for only a single dye concentration. The method uses transient photoluminescence yield measurements, for a wide initial excitation density range. The analysis is applied to an iridium complex and is supported by the results of kinetic Monte Carlo simulations.