Micellar catalysis offers a green alternative method for catalytic transformations by the solubilization of hydrophobic organic compounds. Biosurfactants represent a sustainable alternative to synthetic surfactants due to their biodegradability, low toxicity, and production from renewable feedstocks. In this work, we demonstrated the applicability of biosurfactant rhamnolipids in various micellar cross couplings, and prepared special fluorinated conjugated systems, active pharmaceutical ingredient (API) building blocks and bioactive compounds.