Two new solvates of the dinuclear salt {(η5-C5H5)(CO)2Fe}2(μ-DABCO)](BF4)2 (DABCO = 1,4-diazabicyclo[2.2.2]octane); 1 (D2O solvate) and 2 (acetone solvate), and the mononuclear salt [(η5-C5H5)(CO)2Fe(DABCO)]BF4, 3, have been synthesized and structurally characterized. The D2O solvate, 1 forms crystals in the triclinic space group P1, the acetone solvate forms crystals in the monoclinic P21/c space group, while the unsolvated mononuclear salt, 3, forms crystals in the orthorhombic P212121 space group. The respective unit cell parameters are: Compound 1, a = 7.66300(10) Å, b = 12.3133(2) Å, c = 13.9629(2) Å, α = 69.179(1) °, β = 77.114(1) ° and γ = 84.282(1) °; Compound 2, a = 17.3633(3) Å, b = 14.1688(3) Å, c = 11.3542(2) Å, β = 99.344(1) °; Compound 3, a = 8.9936(2) Å, b = 10.8949(3) Å, c = 15.3417(4) Å. The DABCO ligand adopts a twisted conformation with N-C-C-N torsion angles ranging between -21.05(12) to -19.31(12) ° and 15.3(2) -15.7(2) ° in 1 and 2, respectively, whereas in 3, the CH2 groups of each NCH2CH2N moiety are almost eclipsed, the torsion angles ranging from -2.89(18) to -1.50(16) °.