Conjugated polymers are attractive for many applications due to their unique properties. Their molecular structure can easily be tuned, making them suitable for an enormous number of specific applications. Conjugated polymers have the potential to achieve electrical properties similar to those of noncrystalline inorganic semiconductors; however, their chemical structure is much more complex and somewhat resembles that of biomacromolecules. The molecular conformation and interactions of conjugated polymers play an important role in their functionality. The use of enzymes has emerged as a highly valuable alternative method to synthesize these polymers and is very useful in the fabrication of their nanostructures. Here, we present established strategies for the synthesis of conjugated polymers in template-free systems that do not interfere with the preparation of their nanostructures. These strategies are based on the use of peroxidases (class III; EC 1.11.1.7, donor: hydrogen peroxide oxidoreductase), which are enzymes that have the ability to catalyze the oxidation of a number of compounds (including aromatics such as aniline, pyrrole, thiophene and some of their derivatives), in the presence of hydrogen peroxide, to obtain conjugated polymers.