Synthesis and characterization of a novel type of liquid crystalline thermoset (LCT) based on branched liquid crystalline (LC) bismethacrylate monomers are described. The characteristic structural feature of these branched LC bismethacrylates is the combination of three rigid units, namely a central biphenyl unit, prepared by reaction of 4,4’-dihydroxybiphenyl with glycidyl methacrylate and pendant cyanobiphenyl mesogens, linked to the bismethacrylate via a spacer unit by esterification of the hydroxyl groups. The spacer between pendant mesogens and the central unit was varied. Both branched bismethacrylates with C5 and C11 spacers exhibited the formation of a nematic phase in the temperature range between 10 and 70 degrees C. LC properties were characterized by differential scanning calorimetry, polarizing microscopy, and wide angle X-ray diffraction. LC phases were stable for prolonged periods at ambient temperature. Nonmesagenic model compounds with a central biphenyl segment and C2 as well as C11 side chains that did not form LC phases were also prepared. The LC monomers were oriented by shearing as well as deposition on unidirectionally rubbed polyimide layers and were photo-cross-linked at ambient temperature to ordered thermosets in the LC state. Polarized FT-IR spectroscopy was employed to study the dichroism of the absorption bands in oriented samples of the cross-linked thermosets, which indicated an orientation of the lateral and the central biphenyl units in the drawing direction. Order parameters for cooriented dye were determined before and after cross-linking (0.54 and 0.48, respectively), using polarized UV/vis spectroscopy. Low polymerization shrinkage (2.5%), as well as high moduli, was obtained for the novel LC thermosets.