Electrocrystallization of the bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) organic donor in the presence of the [Fe(ClCNAn)(3)](3-) tris(chlorocyananilato)ferrate(III) paramagnetic anion in different stoichiometric ratios and solvent mixtures afforded two different hybrid systems formulated as [BEDT-TTF](4) [Fe(ClCNAn)(3)]center dot 3H(2)O(1) and [BEDT-TTF](5)[Fe(ClCNAn)(3)](2)center dot 2CH(3)CN (2) (An = anilato). Compounds 1 and 2 present unusual structures without the typical segregated organic and inorganic layers, where layers of 1 are formed by Lambda and Delta enantiomers of the anionic paramagnetic complex together with mixed-valence BEDT-TTF tetramers, while layers of 2 are formed by Lambda and Delta enantiomers of the paramagnetic complex together with dicationic BEDT-TTF dimers and monomers. Compounds 1 and 2 show semiconducting behaviors with room-temperature conductivities of ca. 6 X 10(-3) S cm(-1) (ambient pressure) and 1 X 10(-3) S cm(-1) (under applied pressure of 12.1 GPa), respectively, due to strong dimerization between the donors. Magnetic measurements performed on compound 1 indicate weak antiferromagnetic coupling between high-spin Fe-III(S-Fe = 5 / 2 ) and mixed-valence radical cation diyads (BEDT-TTF)(2)(+) ( S-rad = 1/2) mediated by the anilate ligands, together with an important Pauli paramagnetism typical for conducting systems.