Ba(thd) 2 ( 1) (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) has been synthesized by reacting Hthd both with barium metal and with barium isopropoxide. Compound 1 readily forms the solvated complex [Ba(thd) 2·Et 2O] 2 ( 2), which has been isolated and characterized by elemental analysis, mass spectrometry, IR, 1H and 13C NMR spectroscopy, and single-crystal X-ray structural studies. Compound 2 is a dimeric species in which the two barium atoms are bridged through four oxygen atoms of two β-diketonato ligands, while the other ligands, the remaining two thd − and two Et 2O ligands are coordinated in a terminal mode.