New mesomorphic 1,2,4-oxadiazoles containing o-, m-, and p-bromo-substituents have been synthesized and used as starting compounds in cross-coupling reactions with arylboric acids. This procedure is widely used for synthesis of different biphenyls. For the first time we applied this method to the synthesis of heterocyclic compounds with five-membered oxadiazolic ring. As a result new liquid crystalline oxadiazoles of non linear structure were obtained and characterized by NMR and mesomorphic phase transitions. The cross-coupling reaction with oxadiazoles containing a terminal p-Br-substituent easily provided as main products oxadiazole derivatives containing biphenyl fragments. On the contrary cross-coupling with m-bromo- and especially o-bromo-substituted oxadiazoles due to the steric hindrance was accompanied by a significant number of by-processes.