Due to their good stability and easy structure tailorability, as the typical type of conjugated polymers, polythiophene derivatives have played big role in organo-electronic and renewable energy involved fields. Meanwhile, solid state polymerization attracts lots of attention from researchers because of its advantages of environment benign, large-scale producibility and so on. Thus, in this review, the progresses of thiophene derivatives monomers design and reaction mechanism are reviewed, including their application involved. Furthermore, their opportunities and challenges are discussed as well.