This paper describes a chemical study of a new free-standing ferroelectric liquid crystal film containing a rigid fiber network polymer formed by photopolymerization-induced phase Separation. The liquid crystal and acrylate polymer separated from a homogeneous solution were individually dissolved by different solvents, and examined by high-performance liquid chromatography and gel permeation chromatography, respectively. The liquid crystal component segregated from the solution including 20wt% monomer had a purity of more than 96%, and contained less than 3% of decomposition products and a little remaining monomer, less than 0.3%. The measured molecular weight of the segregated polymer exhibited a broad distribution from 10(3) to 10(6) with a mean polymerization degree of about 100, which increased with monomer concentration. Such a free-standing composite film containing a rigid polymer network is applicable to a shock-resistant ferroelectric liquid crystal display panel because the transparent substrates are supported by the composite film.