Conjugated polymers have received a lot of attention since they combine the best features of metals or semiconductors with those of synthetic polymers. For instance, solar cells based on poly(2,7-carbazole) and poly(thienopyrroledione) derivatives have revealed power conversion efficiencies up to 8-9 %. This class of materials could lead to printable and flexible photovoltaic devices as well as other plastic electronic devices. Along these lines, we will describe novel synthetic methodologies for a simple and “green” preparation of such well-defined conjugated polymers. These new synthetic methods are based on direct (herero)arylation reactions that allow the formation of carbon-carbon bonds between heteroarenes and aryl halides. They do not require organometallic intermediates thereby significantly reducing both synthetic steps, metallic by-products, and cost. They even make possible the synthesis of conjugated polymers that were unknown up to now.