The cholesteryl esters were synthesized from trans-esterification reaction of coconut oil fatty acid methyl esters (FAMEs) with cholesterol using p-toluenesulfonic acid as a catalyst. The optimum condition of trans-esterification reaction of coconut oil with methanol was at 65 ํC for 4 hours. The optimum condition of trans-esterification reaction of FAMEs with cholesterol was at 69 ํC for 6 hours with the 3:33.27 by weight ratio of cholesterol to FAMEs. The synthesized cholesteryl esters, which exhibit liquid crystal property, were characterized for phase transition by DSC. Their structures were identified by FT-IR, GC-MS and 13C-NMR. The obtained cholesteryl esters were dispersed in polyethylene, to form a liquid crystal-polyethylene composite. After that, the composite was extracted with hexane to remove the cholesteryl esters resulted in the formation of aporous film. The porous film was examined by SEM which indicated holes of about 5 mum on polyethylene film.