Organic photovoltaics are a promising low-cost alternative to traditional monocrystalline silicon photovoltaics. The active layer materials are conjugated organic materials, typically polymers. We describe several new series of p-type (donor) conjugated polymers, which we have used to evaluate structure-property relationships in an effort to improve OPV efficiencies. Specifically, our interest was directed towards the effect of fluorination on various conjugated polymers, as this has recently become a valuable tool for modifying polymer electrochemical properties and improving performance. In an effort to reduce the synthetic complexity of such conjugated polymers, decrease cost, and to embrace more environmentally friendly protocols, we have synthesized our materials using newer Direct Arylation Polymerization (DArP) techniques. With DArP, we have synthesized poly(thieno[3,4-b]thiophene-co-benzodithiophene), poly(diketopyrrolopyrrole)s and P(3HT-co-3H4FT)s with high molecular weight, with low percentages of structural defects. Furthermore, we have demonstrated that these materials perform equally to those synthesized by mainstream coupling methods such as GRIM, Stille or Suzuki coupling.