Electrocrystallization of the dianionic Re(IV)F6 species with different organic π electron donors was carried out. Depending on the first oxidation potential of the TTF derivatives this crystallization technique gave rise to various radical cations salts involving Re(IV) or Re(V) anions. With tetramethyltetrathiafulvalene (TMTTF) the (TMTTF)2Re(IV)F6  salt was obtained. However, with tetramethyltetraselenafulvalene (TMTSF) we obtained very small needles of the (TMTSeF)2Re(V)F6 system, analogue to the so called “Bechgaard salts” [1]. We present some characteristics of this new metallic phase. We compare to the diamagnetic (TMTSeF)2Ta(V)F6 obtained by the same strategy using TBATaF6 prepared according to the Browstein’s method [2] and explore electrocrystallization of the tantalum based anions [3], [4]. References: [1] K. Bechgaard, C.S. Jacobsen, K. Mortensen, H.J. Pedersen, N. Thorup, Solid State Commun. 1980, 33, 1119-1125. [2] S. Brownstein, Inorg. Chem. 1973, 12, N°3, 584-589. [3] C. Lenoir, K. Boubekeur, P. Batail, E. Canadell, P. Auban, O. Traetteberg, D. Jérome, Synth. Met. 1991, 42, 1939-1942. [4] F. Iwase, K. Sugiura, K. Furukawa, T. Nakamura, J. Phys. Soc. Jpn. 2009, 78, N°10, 104717:1-104717:7.