Reaction of HORF and in situ synthesized [Ba(ORF)(2)] (from Ba[N(SiMe3)(2)](2)(THF)(2) and HORF) with CuMes yields, in THF, [(THF)(2)Ba2Cu2(OCMe(CF3)(2))(6)]. In the case of HORF = HOCMe2CF3, only upon addition of Me3NO is a soluble product obtained: [(Me3NO)(2)Ba2Cu4(OCMe2CF3)(8)]. [(THF)(2)Ba2Cu2(OCMe(CF3)(2))(6)] has a square-planar Ba2Cu2O4 core structure with two additional alkoxides bridging the two bariums, giving the barium a tbp coordination environment. The structure of [(Me3NO)(2)Ba2Cu4(OCMe2CF3)(8)] is markedly different in that it has one more Cu-(OR) unit inserted into the Ba-(OR)-Ba unit. This gives the Ba2Cu4 core structure the shape of an octahedron and barium a square-pyramidal coordination environment. These structures are compared and contrasted with the structures of [Ba2Cu4(OCEt3)(8)], [(Et3PO)(2)Ba2Cu4((OBu)-Bu-t)(8)], and [(Me3NO)(2)Ba2Cu4((OBu)-Bu-t)8].