In this work, we found that by performing photo-polymerization of the mesogenic monomer RM257 in liquid crystals, well organized polymer walls were formed through out the cell by self-assembly of the polymer within the anisotropic host – the liquid crystal. The polymerization conditions, which were parameterized as UV intensity, photo-reactivity (characterized by photo initiator concentration), curing temperature, monomer concentration and mesophase of the liquid crystal host, were systematically varied. Different liquid crystal host also raised some difference in polymer network. We believe this kind of morphology comes from spinodal decomposition and the anisotropic elastic property of the liquid crystal host. It is found that for RM257 and low molecular weight nematic liquid crystals a monomer concentration of 5% is sufficient to use liquid crystal hosts to work as templates for well structured polymer walls.