Butylvinyl ether, 4-ethoxyphenyl 4-[4-(vinyloxy)butyloxy]benzoate and 4-ethoxyphenyl 4[11-(vinyloxy)-undecyloxy]benzoate have been polymerized using boron trifluoride diethyl etherate and tin tetrachloride as cationic initiator. Polymers produced at different temperatures and with different solvents exhibited different stereoregularities. Dyad resonances were assigned from the beta-methylene absorption in a decoupled C-13 nuclear magnetic resonance spectrum, assuming that the polymerization proceeded according to the first-order Markovian trial. The liquid crystalline side-chain polymers were characterized by differential scanning calorimetry, hot-stage polarized light microscopy and X-ray diffraction in order to study the influence of tacticity on mesomorphism and organization. The polymers based on 4-ethoxyphenyl 4[11-(vinyloxy)undecyloxy]benzoate with different tacticities exhibited the same interdigitated smectic A and B structures. Recorded differences in isotropization temperatures could be attributed to differences in molar mass.