The preparation of the first-and second-generation of nitrilefunctionalized poly(alkylidene imine) dendrimers with the organometallic ruthenium complex [Ru(η 5 -C 5 H 5 )(PPh 3 ) 2 Cl] peripherally attached is described. The reaction of N,NЈ-bis-(cyanomethyl)piperazine (1), N,NЈ-bis [NЈЈ,NЈЈЈ-bis(cyanoethyl)aminoethyl]piperazine (2), or N,N,NЈ, NЈ-tetrakis(cyanoethyl)ethylenediamine (3) with [Ru(η 5 -C 5 H 5 )(PPh 3 ) 2 Cl] (4) in the presence of TlPF 6 gives the new air-stable ruthenium metallodendrimers 5, 6, and 7, respectively. These stable metallodendrimers are easily prepared and represent a novel