Conjugated polymers have garnered a surplus of attention ever since the discovery of their promising and diverse electrical and optical properties. Thus, the term “organic electronics” has arisen due to the vast amount of interest in semiconductor polymeric materials. Of this conjugated polymers family, Polythiophenes and their derivatives remain one of the most highly researched in the “organic electronics” area. Their solubility, processability, high conductivity, low cost and ease of synthesis offer an attractive route towards modifiable semiconductors that can be tailored for specific applications. This chapter will delve into the history of polythiophenes with emphasis on polymerization techniques and synthetic experimental details.