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The nanostructure and thermal behaviour of liquid crystalline oligoester were examined by combination of real-time synchrotron small-angle and wide-angle X-ray scattering methods with differential scanning calorimetry. The synthesized oligoester exhibits ability to form a thermotropic mesophase. It was shown that solid crystalline state is observed in the temperature range 25 to 123ºC and liquid crystalline state between 118-156ºC. The transition temperature determined from dynamic small-angle and wide-angle X-ray scattering experiments agrees very well with the results obtained from differential scanning calorimetry.