Triarylamine derivatives are widely used for hole transport in organic optoelectronic devices, but their excellent solubility in many common solvents limits their use for multi-layer device fabrication from solution. In this work, a novel process to the formation of conjugated triarylamine polymer thin-film networks by crosslinking of thiol-substituted and alkyne-substituted triarylamines is investigated. After deposition of the monomer blend and crosslinking under UV exposure, an insoluble thiol-yne polymer network is formed. The applicability of the thiol-yne polymer network as hole-transport layers is exemplified on organic light-emitting diodes. Its implementation reduces the device degradation as compared to OLEDs comprising hole-transport layers from PEDOT:PSS.