An efficient method for the synthesis of trichlorogermyl complexes is reported involving the insertion of GeCl 2 into the metal-chlorine bond of Group VI transition metal complexes bearing a cyclopentadienyl (Cp) or a pentamethylcyclopentadienyl (Cp * ) ligand. This is demonstrated by the reactions of the complexes (η 5 -C 5 R 5 )M(CO) 3 Cl (1a-1c) (a: R = H, M = Mo, b: R = H, M = W; c: R = Me, M = W) and cis-CpM(CO) 2 (L)Cl (3a, 5b) (3a: M = Mo, L = PMe 3 5b: M = W, L = EtNC) with GeCl 2 (dioxane), which afford selectively the trichlorogermyl complexes (η 5 -C 5 R 5 )M(CO) 3 GeCl 3 (2a-2c) and cis-CpM(CO) 2 (L)GeCl 3 (cis-4a, 6b), respectively. The complex cis-CpMo(CO) 2 (PMe 3 )GeCl 3 (cis-4a) isomerizes in solution and in solid-state to trans-CpMo(CO) 2 (PMe 3 )GeCl 3 (trans-4a). The GeCl 2 -insertion reaction offers a more convenient method for the synthesis of Group VI transition metal trichlorogermyl complexes as shown by a comparison of the syntheses of cis-Cp * W(CO) 2 (EtNC)GeCl 3 (6c) from cis-Cp * W(CO) 2 (EtNC)Cl (5c) and GeCl 2 (dioxane) or from Na[Cp * W(CO) 2 (EtNC)] (7c) and GeCl 4 . The crystal structures of the trichlorogermyl complexes 2a, 2c, trans-4a and 6c are reported.