A method of making a fluorothieno[3,4-b]thiophene derivatives and photovoltaic polymers containing same using 3-bromothiophene-2-carboxylic acid as a starting material. This synthetic route provides an easier synthesis as well as greater yield and a purer product, which produces superior results over the prior art less pure products. The resulting materials can be used in a variety of photovoltaic applications and devices, especially solar cells.