Palladium nanoparticles-polypyrrole composite (Pd/PPy) catalyzes the addition of perfluoroalkyl halides to olefins to produce a variety of products with good yields. An effective fluoroalkylation technique tested with various olefins, fluoroalkyl halides and Pd/PPy was developed. The reaction proceeds highly efficient under mild phosphine-free reaction conditions with different substrates, easy catalyst recycling and provides a general and straightforward access to fluoroalkylated products. Furthermore, we were able to control whether the addition of perfluoroalkyl occurs with various monomer (fluoroalkylated alkene or alkane with R-F and OH moieties) or dimer formation (under electrochemical conditions). [GRAPHICS] .