This research is based on the synthesis and evaluation of novel photo- and chemically-reactive, liquid crystalline monomers (reactive mesogens) with improved charge-transporting properties. Low-molar-mass (LMM) liquid crystalline monomers, based on a series of substituted dibenzothiophenes, thiophenes, [2,2']-bithiophenes, thieno[3,2-b]thiophenes, benzo-2,1,3-thiadiazoles and fluorenes have been synthesised. These materials incorporate photo-polymerisable (non-conjugated diene and methacrylate) and chemically-polymerisable (oxetane) end-groups, attached by aliphatic spacer units of varying length to an aromatic core. These photo- and chemically-polymerisable end-groups are situated at the peripheries of the molecular structure, allowing the potential fabrication of multi-layer, organic semiconductor devices due to the insoluble, cross-linked polymer network obtained after polymerisation of the analogous reactive mesogens (RMs).