Side-chain liquid crystalline ionomers were obtained through alkaline hydrolysis of liquid crystalline polyacrylates. In the case of a polyacrylate bearing a phenyl benzoate moiety in the mesogenic group, partial hydrolysis using sodium hydroxide was found to be highly selective and give the sodium salt of benzoic acid; as for a polyacrylate containing a biphenyl moiety in the side group, a hydrolysis reaction resulted in the sodium salt of acrylic acid. Increasing the content of ionic groups led to a systematic depression of the nematic to isotropic transition temperature. On the other hand, ionic aggregation had little effect on the nematic to isotropic transformation enthalpies as well as the glass transition temperatures of these new materials, in particular for ionomers based on the polyacrylate containing a biphenyl moiety in the side group.