The reaction between Ta(OEt)(5) and 1,1,3,3-tetramethyl-1,3-disiloxanediol, (HOSM2OSMe2OH), leads to new siloxy complexes in which the dimeric nature of Ta(OEt)5 is maintained with both bridging ethoxide and disiloxanediolato bridges. With equal amounts of the reagents, two terminal OEt groups are replaced to form [Ta(OEt)(2)](2)(mu-oEt)(2)-(mu-OSiMe2OSiMe2O)(2), 1, whereas with an excess of diol, the remaining terminal OEt groups are also replaced but with a trisiloxanediolato unit to form [Ta(OSiMe(2)OSiMe(2)OSime(2)O)]2(mu-OEt)2(mu-OSiMe2OSiMe2O)2, 2. Complexes 1 and 2 catalyze the transformation of HOSM2OSM2OH to polysiloxanes. Thermal treatment of 1 results in the formation of a 1:2 mixture of Ta2O5/SiO2; no new phases are observed. The molecular structures of 1 and 2 are confirmed by X-ray crystallography.