AbstractBimolecular exciton‐quenching processes such as triplet–triplet annihilation (TTA) and triplet–polaron quenching play a central role in phosphorescent organic light‐emitting diode (PhOLED) device performance and are, therefore, an essential component in computational models. However, the experiments necessary to determine microscopic parameters underlying such processes are complex and the interpretation of their results is not straightforward. Here, a multiscale simulation protocol to treat TTA is presented, in which microscopic parameters are computed with ab initio electronic structure methods. With this protocol, virtual photoluminescence experiments are performed on a prototypical PhOLED emission material consisting of 93 wt% of 4,4ʹ,4ʺ‐tris(N‐carbazolyl)triphenylamine and 7 wt% of the green phosphorescent dye fac‐tris(2‐phenylpyridine)iridium. A phenomenological TTA quenching rate of 8.5 × 10−12 cm3 s−1, independent of illumination intensity, is obtained. This value is comparable to experimental results in the low‐intensity limit but differs from experimental rates at higher intensities. This discrepancy is attributed to the difficulties in accounting for fast bimolecular quenching during exciton generation in the interpretation of experimental data. This protocol may aid in the experimental determination of TTA rates, as well as provide an order‐of‐magnitude estimate for device models containing materials for which no experimental data are available.