AbstractA practical and efficient synthesis of 4‐(triphenylen‐2‐yl)dibenzothiophene, a phosphorescent host, has been established via ligand‐free palladium on carbon (Pd/C) catalyst mediated Suzuki coupling reaction. The process allowed us to recover and reuse the heterogeneous Pd/C catalyst for cost‐effectiveness with a conversion yield greater than 90 %. Moreover, interesting results on solid‐state studies of the sublimed title material have been captured along with its photo‐physical and electrochemical properties, which are appropriate for its use as a host material. Finally, we have fabricated solution‐processed organic light‐emitting diodes (OLEDs) by using the title material as a host and bis(4‐phenylthieno[3,2‐c]pyridinato‐N,C2′) (acetylacetonate) iridium(III) (PO‐01), as a phosphorescent dopant. The devices exhibited efficiencies of ∼9 cd/A at 1000 cd/m2, and the results were comparable with the traditional host, 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl (CBP).