Thiophene-flanked benzothiadiazole derivatives(DTBTs)have been among the most widely used building blocks for synthesis of a myriad of high-performance conjugated polymers for applications such as optoelectronic devices,sensing and bioimaging.1-3 In this talk,I will present that these building blocks were able to be synthesized via a facile and straightforward method called direct arylation coupling.1 Our optimization of Pd2dba3-catalyzed direct arylation coupling2 gave DTBTs with comparable yield to that of Suzuki or Stille coupling reaction.DTBTs were further polymerized with fluorene dibromide via direct arylation polycondensation to give well-defined alternating polymers.One-pot direct arylation polymerizations were also carried out between benzothiadiazole dibromide,fluorene dibromide and thiophene derivatives,to form DTBTs-containing random copolymers.