Crystal structures of 4-propyloxyphenyl 4-(4-trifluoromethylbenzoyloxy)benzoate (I), p-phenylene 4-methoxy-benzoate 4-trifluoromethylbenzoate (II), ethyl 4-[2-(perfluorooctyl)ethoxy]benzoate (III), and 3-[2-(perfluorooctyl)ethoxy]nitrobenzene (IV) have been determined. All the crystals have smectic-like layer structures. In a layer, molecules are arranged in an antiparallel way in I and II, where CF3 groups are sorrounded by alkyl groups. In III and IV, head-to-head arrangements result in the segregation of perfluorochains and the other moieties in bimolecular layers.