The strong electron-donation and the steric bulk of trialkylphosphines renders them as very useful ligands for palladium-catalyzed cross coupling reactions. This critical review reports on the synthesis of two families of trialkylphosphines (diadamantylalkylphosphines, fluorenyldialkylphosphines) and the properties of the respective palladium complexes in various cross coupling reactions, which evolved as alternatives to the classical Pd/PtBu(3) system. In contrast to the latter phosphine the new classes of ligands are characterized by a highly flexible ligand design, which allows the fine tuning of catalytic properties to the specific needs of certain substrates and also enables the attachment of additional tags to impart certain useful properties onto the respective phosphines (179 references).