AbstractThe photoinitiated bulk polymerization of macroscopically oriented 1,4‐phenylene bis{4‐(ω‐acryloyloxyalkyloxy)benzoate} produces densely crosslinked oriented polymer networks. The influence of the length of the alkylene spacer between the aromatic central core and the polymerizable acrylate end‐groups on the mesomorphic behaviour of the monomer, the molecular orientation in the monomeric and polymeric state and the process of photoinitiated polymerization in the ordered state is studied. Some optical properties of the oriented networks are p