Metathesis reactions between YCl3 and various sodium fluoroalkoxides offered mixed-metal species such as Na3Y[OCH(CF3)(2)](6)(THF)(3) (1), Na2Y[OCMe(CF3)(2)](5)(THF)(3) (2), and Na2Y[OCMe(2)(CF3)](5)(THF) (3). The various compounds have been characterized by NMR, mass spectrometry, and thermogravimetric analysis, in addition to X-ray diffraction investigations for 1 and 2. Compound 1 crystallizes in the space group P $($) over bar$$ 1 with a = 14.479(2) Angstrom, b = 17.155(2) Angstrom, c = 11.209(1) Angstrom, alpha 104.75(1)degrees, beta = 109.48(1)degrees, gamma = 85.23(1)degrees, and Z = 2 while 2 crystallizes in the space group P2(1)/n with a = 13.484(3) Angstrom, b = 15.762(4) Angstrom, c = 22.305(6) Angstrom, beta = 102.42(1)degrees, and Z = 4. The yttrium centers display a distorted octahedral geometry; the surrounding of the Na atoms is composed of bridging fluoroalkoxide oxygens, THF molecules, and secondary Na ... F interactions (2.246(8)-3.323(8) Angstrom) giving rise to coordination numbers of up to 11. Sublimation of Y-Na species proceeds with retention of the stoichiometry between the metals but with loss of the THF ligands.