A new synthetic method of heterobimetallic complexes bridging with a pi,pi-phenylcyclopentadienyl ligand, tricarbonylchromium-eta(6),eta(5)-phenylcyclopentadienyl-transition metal complexes, was developed through the reactions of (eta(6)-C6H5C5H5)Cr(CO)(3) or its sodium salt with transition metal complexes. The method is suitable far most transition metal elements with the advantages of easy manipulation, mild reaction conditions, and moderate to high yields. As indicated by H-1 NMR spectra, the interactions between the two eta systems of phenyl and cyclopentadienyl rings were weak. X-ray crystal structures of seven complexes were studied. Compound 23, [eta(6)-C6H5Cr(CO)(3)](2)C10H10, crystallizes in orthorhombic space group Pbca with cell constants a = 29.616(8) Angstrom, b = 12.861(5) Angstrom, c = 12.397(7) Angstrom, V = 4721(6) Angstrom(3), Z = 8, R = 0.045, and R(w) = 0.035. Compound 3, (eta(6)-C6H5C9H7)Cr(CO)(3), crystallizes in monoclinic space group P2(1)/c with cell constants a = 7.901(3) Angstrom, b = 14.799(2) Angstrom, c = 12.917(2) Angstrom, beta = 99.72(2)degrees, V = 1488.7(4) Angstrom(3), Z = 4, R = 0.044, and R(w) = 0.051. Compound 7, Cr(CO)(3)(eta(6),eta(5)-C6H5C5H4)Ti(CO)(2)(eta(5)-C5H5) crystallizes in monoclinic space group P2(1)/c with cell constants a = 12.361(4) Angstrom, b = 12.387(6) Angstrom, c = 12.531(7) Angstrom, beta = 93.38(4)degrees, V = 1930 Angstrom(3), Z = 4, R = 0.047, and R(w) 0.048. Compound 13, Cr(CO)(3)(eta(6),eta(5)-C6H5C5H5)Mo(CO)(3)Br, crystallizes in monoclinic space group P2(1)/c with cell constants a = 14.685(2) Angstrom, b = 8.509(3) Angstrom, c = 14.960(3) Angstrom, beta = 104.46(1)degrees, V = 1810.0(7) Angstrom(3), Z = 4, R = 0.037, and R(w) = 0.037. Compound 19, Cr(CO)(3)(eta(6),eta(5)-C6H5C9H6)Mo(CO)(3), crystallizes in triclinic space group P-1 with cell constants a = 11.660(4) Angstrom, b = 12.578(5) Angstrom, c = 6.987(2) Angstrom, alpha = 100.03(3)degrees, beta = 104.19(2)degrees, gamma = 71.99(3)degrees, V = 939.3(6) Angstrom(3), Z = 2, R = 0.048, and R(w) = 0.065. Compound 21, Cr(CO)(3)(eta(6),eta(5)-C6H5C5H4)Ru(PPh(3))(2)Cl, crystallizes with one molecule of EtOH in triclinic space group P-1 with cell constants a = 14.033(4) Angstrom, b = 16.163(6) Angstrom, c = 10.411(3) Angstrom, alpha = 104.22(3)degrees, beta = 103.50(2)degrees, gamma = 90.81(3)degrees, V = 2219(1) Angstrom(3), Z = 2, R = 0.081, and R(w) = 0.096. Compound 22, Cr(CO)(3)(eta(6),eta(5)-C6H5C5H4)Co(CO)(2), crystallizes in orthorhombic space group P2(1)2(1)2(1) with cell constants a = 15.083(5) Angstrom, b = 16.391(5) Angstrom, c = 6.351(4) Angstrom, V = 1570(1) Angstrom(3), Z = 4, R = 0.036, and R(w) = 0.039. The trans configurations of the two metal atoms in these molecules were found as expected; the phenyl and cyclopentadienyl or indenyl rings in the molecules were found to be not coplanar.