The synthesis of new chiral smectic A (SA) side-chain liquid crystalline polysiloxanes (LCPs) and ionomers (LCIs) containing 4-allyloxy-benzoyl-4-(S-2-ethylhexanoyl) p-benzenediol bisate (ABB) as mesogenic units and 4-[[4-(2-propenyloxy)phenyl]azo]benzenesulfonic acid (AABS) as nonmesogenic units is presented. The chemical structures of the monomers and polymers are confirmed by FTIR spectroscopy or 1H-NMR. Differential scanning calorimetry (DSC), optical polarizing microscopy, and X-ray diffraction measurements reveal that all the polymers PI-PIV and ionomers PV-PVI exhibit SA texture. The results seem to demonstrate that the tendency toward the SA-phase region increases with increasing sulfonic acid concentration, and the thermal stability of the SA phase is determined by the flexibility of the polymer backbones and the interactions of sulfonic acid groups.