Arene-iron chemistry was applied in the synthesis of a novel liquid crystalline polymer. The chemistry, which is based on iron cyclopentadienyl (FeCp) arene complexes, allows sequential nucleophilic substitution of the chlorides from 1,3-dichlorobenzene-FeCp complex and photolytic decomplexation of the products to afford asymmetrical aryl ethers. This methodology provides easy access to novel polyether-esters, and is potentially useful in the synthesis of various functional polyarylates.