The paramagnetic and chiral anion [Fe(C5O5)(3)](3-) (C5O52- = croconate) has been combined with the organic donor BEDT-TTF (=ET = bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor with the first chirality-induced alpha phase, alpha-(BEDT-TTF)(5)[Fe(C5O5)(3)]center dot 5H(2)O (1), and one of the few known paramagnetic molecular metals, beta-(BEDT-TTF)(5)[Fe(C5O5)(3)]center dot C6H5CN (2). Both compounds present layers of BEDT-TTF molecules, with the alpha or beta packing modes, alternating with layers containing the high-spin S = 5/2 Fe(III) anions and solvent molecules. In the alpha phase, the alternation of the chiral [Fe(C5O5)(3)](3-) anions along the direction perpendicular to the BEDT-TTF chains induces an alternation of the tilt angle of the BEDT-TTF molecules, giving rise to the observed alpha phase. The alpha phase presents a semiconductor behavior with a high room-temperature conductivity (6 S center dot cm(-1)) and an activation energy of 116 meV. The beta phase presents a metallic behavior down to ca. 120 K, where a charge localization takes place with a reentrance to the metallic state below ca. 20 K followed by a metal-semiconductor transition at ca. 10 K. The magnetic properties are dominated by the paramagnetic S = 5/2 [Fe(C5O5)(3)](3-) anion with an extra Pauli-type paramagnetism in the metallic beta phase. The ESR spectra confirm the presence of the high-spin Fe(III)-containing anion and show a progressive localization in the organic sublattice along with an antiferromagnetic coupling below ca. 120 K that, in the metallic beta phase, could be at the origin of the transition from the metallic to the activated conductivity regime. The correlation between crystal structure and conductivity behavior has been studied by means of tight-binding band structure calculations which provide a rationalization of the charge distribution and conductivity results.