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Poly(epichlorohydrin) (PECH) containing pendant mesogenic units separated from the polymer main chain through spacers of zero to ten methylene units were synthesized and characterized. The synthetic pathway used for the chemical modification of PECH involved the phase transfer catalyzed etherification and esterification of the chloromethyl groups with sodium 4-methoxy-4′-biphenoxide and potassium ω-(4-methoxy-4′-oxybiphenyl)alkanoates. All the resulting polymers, including that with no spacer, present thermotropic liquid crystalline mesomorphism.