The reactions of Cp*TiF3 and CpTiF(3) with Me(3)SiOCOCF(3) and Me(3)SiOCOC(6)F(5), respectively lead under elimination of Me(3)SiF in good yields to the dimers (Cp*TiF2OCOCF3)(2) (1), (Cp*TiF2OCOC6F5)(2) (2), (CpTiF(2)OCOCF(3))(2) (3), and (Cp*TiF(OCOCF3)(2))(2) (4). The structures of 1 and 2 have been determined by X-ray crystallography; both compounds crystallize in the triclinic space group P (1) over bar. These are the first examples of dimeric Cp- and Cp*-titanium carboxylates. The Ti atoms are bridged by two carboxylate groups and two F atoms which have nonequal distances to the Ti atoms. The dimeric structures exist also in solution. 1 and 2 show in the F-19 NMR the signals of magnetically nonequivalent bridging and terminal F atoms.