Side-chain liquid crystalline polyelectrolytes containing terminal (cyanobiphenylyl)oxy moieties were obtained through hydrolysis of the corresponding poly(maleic anhydride-co-alkyl vinyl ether)s with spacer lengths of 6-12 methylene groups. All polymers display a liquid crystalline phase. The transition temperatures are lower for the more rigid poly(maleic anhydride-co-alkyl vinyl ether)s. The enthalpy gain associated with the phase transition decreases with increasing rigidity of the polymeric backbone and with decreasing spacer lengths. In aqueous solution all polyelectrolytes have two distinct apparent pK(a) values, 3.3 and 6.5, indicative for strong nearest neighbor interactions within a maleic acid moiety. At neutral pH a blue shift of the absorbance maximum is observed which increases with increasing spacer length. Above pH 8 the blue shift decreases, indicating a conformational transition of the polyelectrolytes from more compact microdomains to a more extended chain conformation.