New thermotropic liquid crystalline poly(malonic ester)s with two symmetrical mesogenic units (paired mesogens) were prepared by the polycondensation of 1,6-dibromohexane and novel malonic ester compounds with different flexible ethyleneoxy spacer lengths linked to azobenzene group. All the prepared malonic esters and the resulting polymers exhibited monotropic liquid crystallinity with a nematic texture. The length of the spacer had influence on the temperature of phase transition of them. A possibility of application of the prepared polymers to reversible optical information storage media was also identified through a trans–cis isomerization of azobenzene by UV irradiation.