As the key building block for highly crosslinked, crystalline polymer networks, we synthesized a novel difunctional liquid crystalline terminal alkene monomer (LCM, Scheme 1). We employ short six-carbon spacer chains to reach a high crosslinking density even with thiol-ene step growth polymerization. A manageable melting point (104 °C) allows processing and 3D printing and is achieved by avoiding a conventional aromatic ether bridge between mesogen and spacer. Instead, a cross-coupling reaction attaches the spacer directly to the core, which we found to reduce the melting point. A fully rod-shaped mesogenic core without side groups ensures a broad LC phase (104-172 °C, Supplementary Figure ), which is particularly important for consistent curing within the LC phase, since adding a non-LC thiol comonomer will reduce the LC temperature range.