The detailed measurement and analysis of the delayed emission from poly(vinylcarbazole) (PVK) and poly(N-ethyl-2-vinyl-carbazole) (P2VK) thin films is described. PVK has rapidly become a “polymer of choice” for hosting phosphorescent dopants in PLEDs, especially blue emitters. In this respect it is important to have a full understanding of the triplet properties of this host. It is concluded that in films, the electronic 0–0 peak energy of PVK phosphorescence is found at 2.88 eV (14 K). With an increase of temperature, >44 K, increasing emission from new long lived, lower energy species, previously ascribed to “trap states” in the literature, is observed. Increasing temperature enables thermally assisted triplet exciton hopping to these trap states. Critically it is shown that some of these triplet trap species are ground state triplet dimers in origin for both PVK (2.46 eV) and P2VK (2.1 eV), and not all of them are of excimer nature as previously thought. These species can quench the emission of blue heavy metal complexes doped in PVK and drastically effect performance over lifetime if the dimer formation increases over time and at elevated operating temperature. It is therefore concluded that PVK might not be such an ideal host material for blue phosphorescent emitters.