This paper deals with the synthesis and thermal properties of seven new high temperature liquid-crystalline thermosets based on maleimide functional group and flexible segments. The melting temperatures are generally lower than 2000C. The crosslinking directly obtained from the liquid crystal state could be achieved only with two bismaleimides. However, crosslinking obtained fromthe isotropic state systematically gives an orderly state. It gives at the end of the reaction a smectic C order. The obtained materials show degradation temperatures higher 4000C and high Tï¤ that can reach 2800C.