Liquid crystalline mixtures of mono- and dimethacrylates were photopolymerized after macroscopic orientation of the monomers under a relatively weak magnetic field or via interaction with a unidirectionally rubbed polyimide substrate. Polymerization kinetics was followed by a thermoanalysis technique, and the transmitted light intensity was measured in realtime. The macroscopic order parameter of one of the component comonomers (bearing a cyano group) incorporated into the polymer network prepared under different conditions was evaluated using IR dichroism. The results obtained for the cross-linked polymer network produced under the low strength magnetic field are compared with those for the polymer film produced by surface orientation.