We report the preparation, structural and physical investigations of BEDT-TTF (ET) salts formulated κ-[Et 4 N](ET) 4 M(CN) 6 , 3 H 2 O (M = Fe I I I , Co I I I , Cr I I I ). These κ-phases show two phase transitions at 240 K and 150 K. The first structural transition, at 240 K, is followed by a redistribution of the charges on the ET molecules and the magnetic and electrical properties are explained on the basis of this phenomenon.