Abstract: A detailed investigation into the influence of phosphines, additives, bases, and solvents on the Heck coupling reaction of 4-trifluoromethyl-1-chlorobenzene (2) is presented. It is shown that a number of catalyst systems exist for efficient cross coupling of electron deficient aryl chlorides with various olefins. Basicity and steric demand of the ligand are two factors which determine the success of the reaction. In addition the phosphine / palladium ratio, the correct type and amount of additive, and finally the use of an appropriate base and solvent are also important. The optimised reaction conditions are applied for the arylation of styrene, butyl vinyl ether, and N,N-dimethyl acrylic amide with various aryl chlorides.