The synthesis of side-chain liquid crystalline polyoxetanes containing 4-(alkanyloxy)phenyl trans-4-alkylcyclohexanoate side groups is presented. Differential scanning calorimetry, optical polarizing microscopy, and X-ray diffraction measurements reveal polymorphism of mesophases for all obtained polymers. Both spacer length and terminal alkyl length have a profound influence on the nature and thermal stability of the mesophases. Although the polyoxetane backbone is more flexible than the polymethacrylate backbone, side-chain crystallization did not occur for any of the synthesized polymers.