Three new molecular charge transfer salts of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF), (BEDT-TF)(4)AFe(C2O4)(3)C6H5CN (A = H2O, K, NH4), have been prepared, and their crystal structures and physical properties determined. The structures of all three salts consist of successive layers of BEDT-TTF and layers of approximately hexagonal geometry containing alternating A and Fe(C2O4)(3)(3-), with C6H5CN lying within the hexagonal cavities. When A = K or NH4 the BEDT-TTF layers consist of dimers (BEDT-TTF)(2)(2+) separated by isolated (BEDT-TTF)(0), the charge difference being estimated from the C=C and C-S bond lengths. These salts are semiconductors to (sigma similar to 10(-4) S cm(-1), E(A) = 0.14 eV), and their magnetic susceptibilities are dominated by S = (5)/Fe-2(III). The EPR spectra accordingly show only one sharp signal. When A = H2O the BEDT-TTF adopt the beta " packing, and the salt is a superconductor (T-c 7.0(3) K). The magnetic susceptibility above the critical temperature is the sum of a Pauli component (2 x 10(-3) emu mol(-1)) and a Curie-Weiss term. Below the transition the susceptibility depends on the field penetration according to the London penetration depth, increasing with increasing field until the critical field. The Meissner effect is almost complete, indicating absence of pinning. The EPR spectra of the A = H2O compound are characterized by two resonances, one of Dysonian shape due to the conduction electrons on the organic cations and the other of Lorentzian shape arising from the 3d electrons of Fe-III. Electronic band structure calculations suggest that the A = K compound is semiconducting (E(g) = 0.3 eV) in good agreement with that result obtained from electrical measurement and the A = H2O is metallic (W = 1.1 eV) with both electron and hole pockets in the Fermi surface. Optical reflectivity of the latter gives an electronic bandwidth of 1.0 eV, fully consistent with the band structure calculation.