Abstract A novel series of two-dimensional π-conjugated oligoarylenes has been synthesized by a divergent approach using Pd-catalysed Suzuki cross-coupling of tetraiodophenylbenzene and arylboronic acid as a key step. It has been shown that the ‘X-branched’ structure can provide a useful platform to construct amorphous molecular materials as it can enhance the morphological and thermal stability as well as to facilitate solubility and processibility of a material when compared to those of the corresponding linear oligomers. The diphenylamino end-capped two-dimensional oligoarylenes were found useful as a hole transporting/emitting layer for light emitting applications.