A new kind of codendrimer consisting of a Fréchet-type dendron and a Tomalia-type PAMAM dendron has been synthesized via a liquid-phase approach, which could easily be purified using a simple precipitation method without the need for chromatographic separation. Functionalization at the periphery of a PAMAM dendron with bis(diphenylphosphinomethyl)amino groups led to a novel class of Janus dendritic phosphines. Their use as a recyclable homogeneous catalyst has been demonstrated with the Pd-catalyzed Suzuki coupling reaction.