The synthesis, crystal structure, Raman spectra, XP spectra, conductivity and magnetism of a charge-transfer salt of BEDT-TTF and oxalato-metalate: (BEDT-TTF)5Fe(C2O4)3(H2O)2CH2Cl2 (1) are described and interpreted. Electrochemical oxidation of neutral BEDT-TTF in the presence of (Et4N)3Fe(C2O4)3 in CH2Cl2 solution yields crystals of 1. 1 crystallizes in triclinic form with cell parameters: a = 11.0197(1)Å, b = 11.5010(2) Å, c = 35.2773(5) Å, α = 89.1256(4)°, β = 85.2348(5)°, γ = 70.0039(4)°, V = 4186.5(1) Å3, Z = 2, P in 180 K. 1 is different from the well known charge-transfer salt (BEDT-TTF)4AM(C2O4)3S (A = K+, NH4+ and H3O+, S = solvent) in composition and crystal structure. Two donor layers and anion layers stack alternately along the c axis in 1. There is one enantiomer in an anion layer and the crystal remains racemized. The solvent molecule H2O bonds to two anions through hydrogen bonds and CH2Cl2 exists in the cavity of the parallelogram formed by anions but not a pocket of honeycomb of [AM(C2O4)3]2− as in (BEDT-TTF)4AM(C2O4)3S. The formal charge of donor molecules was assigned to +0.5 and +1.0 from bond lengths in TTF core and corresponded to Raman and XP spectra. 1 is a paramagnetic semiconductor with σrt = 4 S cm−1.