The synthesis and characterization of new bis‐cyclometalated complex salts [M(ptpy)2(2,2’‐biphenyldiamine)]PF6 (M=Rh, 1; M=Ir, 2; ptpy=2‐(p‐tolyl)pyridinato) are described. Compounds 1 and 2 were obtained by bridge‐splitting reactions of [{M(μ‐Cl)(ptpy)2}2] (M=Rh or Ir) with 2,2’‐biphenyldiamine in CH2Cl2/MeOH/H2O mixtures. The molecular structure of compound 2 in the crystal was confirmed by single‐crystal X‐ray
diffraction. 2 crystallized from dichloromethane/methanol/n‐heptane in the monoclinic space group P21/n. The cytotoxic activities of both new compounds were examined and evaluated. Compound 1 and 2 exhibit significant cytotoxicity against human cancer cell lines with the IC50 values in the low micromolar range.