SUMMARY:The mesomorphic properties and thermal stability of side-chain LC polycarbonates with alkoxyphenyl benzoate side groups having a short spacer and alkoxy tails ranging from 1 to 8 carbon atoms were studied by DSC, X-ray diffraction and polarized light optical microscopy. All polymers have a smectic A structure. Mesogens having short tails organize preferably in a monolayer structure, and mesogens having long tails in a double layer structure. A sharp increase in the clearing temperatures and enthalpies as a function of tail length was observed. No clear relation between the tail length and the glass transition temperature was found. Both the T g and the clearing temperature show a strong dependence on the molecular weight. Up to about M -w = 20 000 a rapid increase in phase transition temperatures with increasing molecular weight was observed, eventually levelling off to a constant maximum value. The LC polycarbonates were found to be thermally stable up to about 200 8C. At higher temperatures, random chain scission, resulting in a rapid decrease in molecular weight, and unzipping, resulting in the formation of a five-membered cyclic carbonate, are the main initial degradation mechanisms. The degraded polymers have lower transition temperatures than the original ones.